CN117794915A

CN117794915A - Compound, material for organic electroluminescent device comprising the same, and organic electroluminescent device

Info

Publication number: CN117794915A
Application number: CN202280054116.6A
Authority: CN
Inventors: 米歇尔·格罗克; 娜塔莉亚·切博塔列娃; 丰岛弘明; 齐藤雅俊; 水谷清香; 三谷真人
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2021-08-26
Filing date: 2022-08-25
Publication date: 2024-03-29
Also published as: EP4140994A1; KR20240052749A; WO2023027196A1

Abstract

A specific compound represented by formula (I), a material for an organic electroluminescent device comprising the specific compound, an electronic apparatus comprising the organic electroluminescent device, and use of the compound in an organic electroluminescent device.

Description

Compound, material for organic electroluminescent device comprising the same, and organic electroluminescent device

Technical Field

The present invention relates to a specific compound, a material for an organic electroluminescent device comprising the specific compound, an electronic apparatus comprising the organic electroluminescent device, and the use of the compound in an organic electroluminescent device.

Background

When a voltage is applied to an organic electroluminescent device (hereinafter may be referred to as an organic EL device), holes are injected from an anode to an emission layer, and electrons are injected from a cathode to the emission layer. In the emission layer, the injected holes and electrons recombine and form excitons.

The organic EL device includes an emissive layer between an anode and a cathode. Further, there may be a case where it has a stacked layer structure including an organic layer such as a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, or the like.

WO2012/105629A1 relates to a nitrogen-containing heterocyclic derivative of formula (1), an electron transporting material for an organic electroluminescent device, and an organic electroluminescent device employing the electron transporting material.

A ₁ (-L ₁ -L ₂ -L ₃ -L ₄ -Ar ₁ ) _m (1)

Wherein A1 represents an m-valent residue of a compound having a cyclic structure represented by the following formula (2), and m represents an integer of 1 or more.

WO2016/128103 A1 relates to an electronic device, in particular an organic electroluminescent device, comprising a specific cyclic lactam of the following formula (1) comprising at least two carbonyl groups, and to a specific cyclic lactam for use in an electronic device, in particular an organic electroluminescent device.

Wherein Y is in each case

WO2013/064206A1 relates to electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (1), to specific compounds of formula (1) and to processes for preparing these compounds.

Wherein Y is-C (═ O) -N (Ar 1) -, -C (═ O) -O-, -CR1 ═ CR 1-; -CR1 ═ N-, C (R1) 2, NR1, O, S, C (═ O) C (═ S), C (═ NR 1), C (═ C (R1) 2), si (R1) 2, BR1, PR1, P (═ O) R1, SO or SO2.

CN110003116 a relates to an organic photoelectric material containing a cyclic urea structure according to general formula (I)

Wherein A is selected from one of the following structural groups:and is also provided with

R ¹ To R ³ Independently selected from hydrogen, methyl, ethyl, C ₆ -C ₃₀ Polycyclic aryl conjugated groups, or C containing hetero atoms, e.g. N, S or O ₄ To C ₃₀ Any of the polycyclic aryl conjugated groups.

The organic photoelectric material containing the cyclic urea structure is applied to CPL (=cap layer) of an organic electroluminescent device according to CN110003116 a.

List of references

Patent literature

WO 2012/105629 A1

WO 2016/128103 A1

WO 2013/064206 A1

CN 110003116 A

Disclosure of Invention

Technical problem

The specific structure and substitution pattern of the compounds in the organic electronic device have a significant impact on the performance of the organic electronic device.

Thus, despite the above developments, there remains a need for organic electroluminescent devices comprising new materials, especially charge transporting materials (e.g. electron transporting materials), charge blocking materials (e.g. hole blocking materials) and/or dopant materials, more especially electron transporting materials, to provide improved performance of electroluminescent devices.

It is therefore an object of the present invention, with respect to the aforementioned related art, to provide additional materials suitable for use in organic electroluminescent devices and additional applications in electronics. More particularly, it should be possible to provide charge transport materials, such as electron transport materials, and/or charge blocking materials, such as hole blocking materials, and/or dopant materials for organic electroluminescent devices. These materials should be particularly suitable for organic electroluminescent devices comprising at least one emitter, which is a phosphorescent emitter and/or a fluorescent emitter.

Furthermore, the material should be suitable for providing an organic electroluminescent device which ensures good overall performance of the organic electroluminescent device, in particular long life, high efficiency and/or low driving voltage.

Solution to the problem

The object is solved by a compound represented by formula (I):

wherein the method comprises the steps of

Y represents NR ¹⁰ 、CR ⁸ R ⁹ O or S, preferably NR ¹⁰ ；

R ¹⁰ Represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms;

R ⁸ and R is ⁹ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms;

or alternatively

R ⁸ And R is ⁹ Taken together form a substituted or unsubstituted carbocyclic or heterocyclic ring;

R ¹ and R is ² Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms, or CN;

R ³ Represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms;

R ⁴ 、R ⁵ 、R ⁶ and R is ⁷ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms, or CN; or alternatively

Selected from R ⁴ And R is ⁵ 、R ⁵ And R is ⁶ Or R is ⁶ And R is ⁷ Together form a substituted or unsubstituted carbocyclic or heterocyclic ring;

wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of which is a bonding site;

X ¹ represents N or CR ¹¹ ；

X ² Represents N or CR ¹² ；

X ³ Represents N or CR ¹³ ；

Wherein X is ¹ 、X ² And X ³ At least one, preferably at least two, of which is N;

R ¹¹ 、R ¹² and R is ¹³ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms;

Or alternatively

R ¹ And R is ¹¹ And/or R ¹² The method comprises the steps of carrying out a first treatment on the surface of the And/or R ² And R is ^-11 And/or R ¹³ May together form a substituted or unsubstituted carbocyclic or heterocyclic ring;

l represents an unsubstituted or substituted divalent aromatic hydrocarbon group containing 6 to 30 ring atoms or an unsubstituted or substituted divalent heteroaryl group containing 3 to 30 ring atoms;

m represents 1, 2, 3 or 4, preferably 1, 2 or 3, where these radicals L are identical or different in the case where m is > 1.

The specific compounds according to the invention of formula (I) can be used as materials which are highly suitable for organic electroluminescent devices, in particular as host, charge transport or charge blocking materials, preferably as electron transport materials. Furthermore, thermally stable compounds are provided, which in particular lead to organic electroluminescent devices having good overall properties, in particular long life, high efficiency and/or low driving voltages.

The compound of the present invention can also be used for other organic electronic devices other than organic electroluminescent devices, such as electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (oled FETs), image sensors, and dye lasers.

Accordingly, another subject of the present invention relates to an organic electronic device comprising a compound according to the invention. The organic electronic device is preferably an organic electroluminescent device (EL device). In the present application, the term organic EL device (organic electroluminescent device) is used interchangeably with the term Organic Light Emitting Diode (OLED).

The compounds of the formula (I) can in principle be used in any layer of an EL device, but are preferably used as charge transport (in particular electron transport), charge blocking (in particular hole blocking) materials. In particular, the compounds of formula (I) are used as electron transport materials and/or hole blocking materials for phosphorescent or fluorescent emitters. Most preferably, the compounds of formula (I) are used as electron transport materials for phosphorescent or fluorescent emitters.

Accordingly, another subject of the invention relates to a material for organic electroluminescent devices comprising at least one compound of formula (I) according to the invention.

Another subject of the invention relates to an organic electroluminescent device comprising an organic thin film layer between a cathode and an anode, wherein the organic thin film layer comprises one or more layers and comprises a light-emitting layer, and at least one layer of the organic thin film layer comprises at least one compound of formula (I) according to the invention.

Another subject of the invention relates to an electronic apparatus comprising an organic electroluminescent device according to the invention.

Another subject of the invention relates to the use of the compounds of formula (I) according to the invention in organic electroluminescent devices. In such embodiments, the compounds of formula (I) are preferably used in the electron transport region of an organic electroluminescent device. Within the meaning of the present invention, the electron transport region comprises at least an electron transport layer and preferably also an electron injection layer and/or a hole blocking layer.

Another subject of the invention relates to an emissive layer comprising a compound of formula (I) according to the invention.

Another subject of the invention relates to an electron transport layer comprising a compound of formula (I) according to the invention. Preferably, the electron transport layer is disposed between the cathode and the light emitting layer of an EL device such as an OLED.

Another subject of the invention relates to a hole blocking layer comprising a compound of formula (I) according to the invention. Preferably, the hole blocking layer is disposed between an electron transport layer and a light emitting layer of an EL device such as an OLED.

Advantageous effects of the invention

The compounds of the invention are suitable for providing organic electroluminescent devices which ensure good performance of the organic electroluminescent devices, in particular high external quantum efficiency, long lifetime and/or low driving voltage.

Drawings

Fig. 1 shows a schematic configuration of one example of an organic EL device of the present invention.

Detailed Description

The terms unsubstituted or substituted divalent aromatic hydrocarbon group containing from 6 to 30 ring atoms, unsubstituted or substituted divalent heteroaryl group containing from 3 to 30 ring atoms, unsubstituted or substituted aromatic hydrocarbon group containing from 6 to 30 ring atoms, unsubstituted or substituted heteroaryl group containing from 3 to 30 ring atoms, unsubstituted or substituted alkyl group having from 1 to 25 carbon atoms, unsubstituted or substituted cycloalkyl group having from 3 to 18 ring carbon atoms are known in the art and generally have the following meanings if the groups are not further specified in the specific embodiments mentioned below:

unsubstituted or substituted aromatic hydrocarbon groups containing 6 to 30 ring atoms, preferably 6 to 24 ring atoms, more preferably 6 to 18 ring atoms may be non-condensed aryl groups or condensed aryl groups. Specific examples thereof include phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, tetrabiphenyl, fluoranthenyl, triphenylene, phenanthryl, fluorenyl, anthracenyl,radicals, spirofluorenyl radicals, 9-diphenylfluorenyl radicals, 9' -spirodi [ 9H-fluorenyl radicals]-2-yl, 9-dimethylfluorenyl and benzo [ c ] ]Phenanthryl, benzo [ a ]]Triphenylene, naphtho [1,2-c]Phenanthryl, naphtho [1,2-a ]]Triphenylene, dibenzo [ a, c]Triphenylene and benzo [ a ]]Fluorescent-anthracenyl, benzo [ j ]]Fluorescent anthracenyl and benzo [ k ]]Fluorescent anthracenyl and benzo [ b ]]Fluorescent-anthracenyl, wherein phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylenyl, fluorenyl, spirobifluorenyl, anthracenyl and fluoranthenyl are preferred, and phenyl, 1-naphthyl, 2-naphthyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, phenanthren-9-yl, phenanthren-3-yl, phenanthren-2-yl, triphenylen-2-yl, 9-dimethylfluoren-4-yl, 9-diphenylfluoren-2-yl, 9-diphenylfluoren-4-yl, fluoranthen-3-yl, fluoranthen-2-yl, fluoranthen-8-yl, anthracene-3-yl and anthracene-9-yl are most preferred.

Unsubstituted or substituted heteroaryl groups containing 3 to 30 ring atoms, preferably 5 to 18 ring atoms, may be non-fused heteroaryl groups or fused heteroaryl groups. Specific examples thereof include a pyrrole ring, an isoindole ring, an imidazopyridine ring, an imidazopyrimidine ring, an imidazopyrazine ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, a dibenzothiophene ring, an isoquinoline ring, a quinoxaline ring, a quinazoline, a phenanthridine ring, a phenanthroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indole ring, a quinoline ring, an acridine ring, a carbazole ring, a furan ring, a thiophene ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a dibenzofuran ring, a triazine ring, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring, a triazole ring, and an imidazole ring, with the residues of the dibenzofuran ring, carbazole ring, and dibenzothiophene ring being preferred, and the residues of the imidazo [1,2-a ] pyridine, imidazo [1,5-a ] pyridine, dibenzofuran-1-yl, dibenzofuran-3-yl, dibenzofuran-2-yl, dibenzofuran-4-yl, 9-phenylcarbazole-3-yl, 9-phenylcarbazole-2-yl, dibenzofuran-4-yl, and more preferred dibenzothiophene-3-yl.

Examples of unsubstituted or substituted alkyl groups having 1 to 25 carbon atoms, preferably 1 to 8 carbon atoms, are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl and 1-methylpentyl.

Further preferred are alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, neopentyl and 1-methylpentyl, with methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl being preferred.

Alkyl groups are unsubstituted or substituted with one or more of the substituents mentioned below. One particular class of preferred substituted alkyl groups is aryl-substituted alkyl groups, i.e., unsubstituted or substituted aralkyl groups. Suitable aralkyl groups are mentioned below. One preferred example is benzyl.

Examples of unsubstituted or substituted cycloalkyl groups having 3 to 18 ring carbon atoms, preferably 3 to 12 ring carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and adamantyl. Most preferred are cycloalkyl groups having 3 to 6 ring carbon atoms, i.e. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The term "unsubstituted or substituted divalent aromatic hydrocarbon group" has the following meaning according to the present invention:

unsubstituted divalent aromatic hydrocarbon radicals are aromatic hydrocarbon radicals which contain two bonding sites to adjacent groups, but no further substituents, i.e. all other possible bonding sites in the groups are substituted by hydrogen.

A substituted divalent aromatic hydrocarbon radical is an aromatic hydrocarbon radical which comprises two bonding sites to adjacent groups but additionally comprises at least one further substituent, i.e. at least one of the other possible bonding sites in the group is substituted by a residue other than hydrogen. Suitable substituents are mentioned below.

The unsubstituted or substituted divalent aromatic hydrocarbon group having 6 to 30 ring atoms, preferably 6 to 18 ring atoms, more preferably 6 to 14 ring atoms may be a non-condensed or condensed divalent aromatic hydrocarbon group. Specific examples thereof include phenylene, naphthylene, biphenylene, terphenylene, tetraphenylene, fluoranthene-diyl, triphenylene-diyl, phenanthrene-diyl, fluoren-diyl, anthracene-diyl, -diyl, spirofluorene-diyl, 9-diphenylfluorene-diyl, 9' -spirodi [ 9H-fluorene ]]-2-diyl, 9-dimethylfluoren-diyl, benzo [ c ]]Phenanthrene-diyl, benzo [ a ]]Triphenylene-diyl, naphtho [1,2-c]Phenanthrene-diyl, naphtho [1,2-a]Triphenylene-diyl, dibenzo [ a, c]Triphenylene-diyl, benzo [ a ]]Fluoranthene-diyl, benzo [ j ]]Fluoranthene-diyl, benzo [ k ]]Fluoranthene-diyl and benzo [ b ]]Fluoranthene-diyl, among which phenylene, naphthylene, biphenylene, terphenylene, phenanthrene-diyl, triphenylene-diyl, fluorene-diyl, spirobifluorene-diyl, anthracene-diyl and fluoranthene-diyl are preferable.

The term "unsubstituted or substituted divalent heteroaryl" has the following meanings according to the invention:

unsubstituted divalent heteroaryl is heteroaryl that contains two bonding sites to adjacent groups, but no additional substituents, i.e., all other possible bonding sites in the group are substituted with hydrogen.

A substituted divalent heteroaryl group is a heteroaryl group comprising two bonding sites to adjacent groups, but additionally comprising at least one further substituent, i.e. at least one of the other possible bonding sites in the group is substituted with a residue other than hydrogen. Suitable substituents are mentioned below.

Unsubstituted or substituted divalent heteroaryl groups containing 3 to 30 ring atoms, preferably 5 to 18 ring atoms, may be non-fused heteroaryl groups or fused heteroaryl groups. Specific examples thereof include pyrrol-diyl, isoindol-diyl, benzofurandiyl, isobenzofurandiyl, benzothiophen-diyl, dibenzothiophen-diyl, isoquinoline-diyl, quinoxaline-diyl, quinazolin-diyl, phenanthridine-diyl, phenanthroline-diyl, pyridine-diyl, pyrazine-diyl, pyrimidine-diyl, pyridazine-diyl, indole-diyl, quinoline-diyl, acridine-diyl, carbazole-diyl, furan-diyl, thiophene-diyl, benzoxazole-diyl, benzothiazole-diyl, benzimidazole-diyl, dibenzofuran-diyl, triazine-diyl, oxazol-diyl, oxadiazol-diyl, thiazole-diyl, thiadiazole-diyl, triazole-diyl, and imidazole-diyl, with dibenzofuran-diyl, carbazole-diyl and dibenzothiophene-diyl residues being preferred.

Examples of the one or more optional substituents indicated by the above or below mentioned "substituted or unsubstituted" and "which may be substituted" include halogen atom, cyano group, alkyl group having 1 to 25, preferably 1 to 8 carbon atoms, cycloalkyl group having 3 to 18, preferably 3 to 12 ring carbon atoms, alkoxy group having 1 to 25, preferably 1 to 8 carbon atoms, alkylamino group having 1 to 25 carbon atoms, preferably 1 to 5 carbon atoms, carboxyalkyl group having 1 to 25 carbon atoms, preferably 1 to 5 carbon atoms, silyl group, C ₆ To C ₂₄ Aryl, preferably C ₆ To C ₁₈ Aryl, aryloxy having from 6 to 24, preferably from 6 to 18, ring carbon atoms, aralkyl having from 7 to 24, preferably from 7 to 20, alkylthio having from 1 to 25, preferably from 1 to 5, arylthio having from 6 to 24, preferably from 6 to 18, ring carbon atoms, arylamino having from 6 to 30, preferably from 6 to 18, carboxyaryl having from 6 to 24, preferably from 6 to 18, carboxamide aryl having from 6 to 24, preferably from 6 to 18, carbon atoms in its aryl, diaryl phosphine oxide groups having from 6 to 24, preferably from 6 to 18, carbon atoms in each aryl, heteroaryl having from 3 to 30, preferably from 5 to 18, ring atoms. These substituents may in turn be unsubstituted or substituted, preferably unsubstituted.

Alkyl having 1 to 25, preferably 1 to 8, carbon atoms, C ₆ To C ₂₄ Aryl, preferably C ₆ To C ₁₈ Aryl and cycloalkyl having 3 to 18 ring carbon atoms, preferably 3 to 12 ring carbon atoms, are as defined above.

Examples of alkenyl groups having 2 to 25 carbon atoms include those disclosed as alkyl groups having 2 to 25 carbon atoms, but containing at least one double bond, preferably one, or, where possible, two or three double bonds.

Examples of alkynyl groups having 2 to 25 carbon atoms include those disclosed as alkyl groups having 2 to 25 carbon atoms, but containing at least one triple bond, preferably one, or, where possible, two or three triple bonds.

Silyl groups are alkyl and/or aryl substituted silyl groups. Examples of the alkyl-and/or aryl-substituted silyl group include alkylsilyl groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, including trimethylsilyl, triethylsilyl, tributylsilyl, dimethylethylsilyl, t-butyldimethylsilyl, propyldimethylsilyl, dimethylisopropylsilyl, dimethylpropylsilyl, dimethylbutylsilyl, dimethylt-butylsilyl, diethylisopropylsilyl, alkylaryl silyl having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms in the aryl moiety and 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms in the alkyl moiety, including phenyldimethylsilyl, diphenylmethylsilyl, diphenylt-butylsilyl, and arylsilyl having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, including triphenylsilyl, with trimethylsilyl, triphenylsilyl, diphenylt-butylsilyl, and t-butyldimethylsilyl being preferred.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of alkylamino (alkyl-substituted amino), preferably alkylamino having 1 to 25 ring carbon atoms, include those having an alkyl moiety selected from the above mentioned alkyl groups.

Examples of arylamino groups (aryl-substituted amino groups), preferably arylamino groups having 6 to 24 ring carbon atoms, include those having an aryl moiety selected from the aromatic hydrocarbon groups mentioned above.

Examples of optionally substituted aralkyl groups having 6 to 30 ring carbon atoms include benzyl, 2-phenylpropane-2-yl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, a-naphthylmethyl, 1-a-naphthylethyl, 2-a-naphthylethyl, 1-a-naphthylisopropyl, 2-a-naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, 1-pyrrolylmethyl, 2- (1-pyrrolylethyl) ethyl p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl.

Examples of carboxyalkyl groups (alkyl substituted carboxyl groups), preferably carboxyalkyl groups having 1 to 25 carbon atoms, preferably 1 to 5 carbon atoms, include those having an alkyl moiety selected from the above mentioned alkyl groups.

Examples of carboxyaryl (aryl-substituted carboxy), preferably having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, include those having an aryl moiety selected from the aromatic hydrocarbon groups mentioned above.

Examples of the carboxyamidoalkyl group (alkyl-substituted amide group), preferably a carboxyamidoalkyl group having 1 to 25 carbon atoms, preferably 1 to 5 carbon atoms, include those having an alkyl moiety selected from the above-mentioned alkyl groups.

Examples of carboxamide aryl groups (aryl-substituted amide groups), preferably carboxamide aryl groups having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, include those having an aryl moiety selected from the aromatic hydrocarbon groups mentioned above.

Examples of the diaryl phosphine oxide groups, preferably having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms in each aryl group, include those having an aryl moiety selected from the above-mentioned aromatic hydrocarbon groups.

The optional substituents are preferably halogen atoms, cyano groups, diaryl phosphine oxide groups having 6 to 18 carbon atoms in each aryl group, alkyl groups having 1 to 25 carbon atoms, aryl groups having 6 to 24 ring carbon atoms, preferably 6 to 18 ring carbon atoms, and heterocyclic groups having 3 to 30 ring atoms, preferably 5 to 18 ring atoms; more preferred are cyano, diphenyl phosphine oxide groups, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, fluorenyl, spirobifluorenyl, fluoranthenyl, dibenzofuran ring-based residues, carbazole ring-based residues, and dibenzothiophene ring-based residues, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopentyl and cyclohexyl.

The optional substituents mentioned above may be further substituted with one or more of the optional substituents mentioned above.

The number of optional substituents depends on the group substituted with the substituent or substituents. Preferably 1, 2, 3 or 4 optional substituents, more preferably 1, 2 or 3 optional substituents, most preferably 1 or 2 optional substituents. In another preferred embodiment, the above mentioned groups are unsubstituted.

The "carbon number of a to b" in the expression of "substituted or unsubstituted X group having a to b carbon atoms" is the carbon number of the unsubstituted X group and does not include one or more carbon atoms of an optional substituent.

The hydrogen atoms mentioned herein include isotopes having different neutron numbers, i.e. light hydrogen (protium), heavy hydrogen (deuterium) and tritium.

A compound of formula (I)

Y represents NR ¹⁰ 、CR ⁸ R ⁹ O or S, preferably NR ¹⁰ 。

R ¹⁰ Represents hydrogen, unsubstituted or substituted aromatic hydrocarbon groups having 6 to 30 ring atoms, cyclic groups having 3 to 30 ring atomsUnsubstituted or substituted heteroaryl of a child, unsubstituted or substituted alkyl having 1 to 25 carbon atoms, or unsubstituted or substituted cycloalkyl having 3 to 18 ring carbon atoms; unsubstituted or substituted aromatic hydrocarbon groups having 6 to 18 ring atoms, unsubstituted or substituted heteroaryl groups having 3 to 18 ring atoms, unsubstituted or substituted cycloalkyl groups having 5 to 8 ring carbon atoms or unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclohexyl, phenyl, biphenyl, naphthyl, pyridyl, quinoline or phenanthroline; more preferably methyl, ethyl, n-propyl, isopropyl, phenyl, naphthyl, pyridinyl or quinoline.

R ⁸ And R is ⁹ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms; unsubstituted or substituted aromatic hydrocarbon groups having 6 to 18 ring atoms, unsubstituted or substituted heteroaryl groups having 3 to 18 ring atoms, unsubstituted or substituted cycloalkyl groups having 5 to 8 ring carbon atoms or unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclohexyl, phenyl, biphenyl, naphthyl, pyridyl, quinoline or phenanthroline; more preferably methyl, ethyl, n-propyl, isopropyl, phenyl, naphthyl, pyridinyl or quinoline;

or alternatively

R ⁸ And R is ⁹ Together form a substituted or unsubstituted carbocyclic or heterocyclic ring, preferably an unsubstituted or substituted carbocyclic or heterocyclic 5 or 6 membered ring.

The compounds of formula (I) are therefore preferably represented by formula (Ia):

wherein the residues, groups and indices are as described above and below.

R ³ Represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms; unsubstituted or substituted aromatic hydrocarbon groups having 6 to 18 ring atoms, unsubstituted or substituted heteroaryl groups having 3 to 18 ring atoms, unsubstituted or substituted cycloalkyl groups having 5 to 8 ring carbon atoms or unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclohexyl, phenyl, biphenyl, naphthyl, pyridyl, quinoline or phenanthroline; more preferably methyl, ethyl, n-propyl, isopropyl, phenyl, naphthyl, pyridinyl or quinoline.

R ¹ And R is ² Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms, or CN; preferably R ¹ And R is ² Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group containing 6 to 30 ring atoms, or an unsubstituted or substituted heteroaryl group containing 3 to 30 ring atoms; more preferably, R ¹ And R is ² Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, such as phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, spirofluorenyl, 9-diphenylfluorenyl, 9' -spirodi [ 9H-fluorenyl]-2-yl, 9-dimethylfluorenyl; even more preferably, R ¹ And R is ² Each independently represents an unsubstituted aromatic hydrocarbon group having 6 to 30 ring atoms, an aromatic hydrocarbon group having 6 to 30 ring atoms substituted with an aromatic hydrocarbon group having 6 to 30 ring atoms, an aromatic hydrocarbon group having 6 to 30 ring atoms substituted with a heteroaryl group having 3 to 30 ring atoms, or an unsubstituted heteroaryl group having 3 to 30 ring atoms; even more preferably, R ¹ And R is ² Each independently represents an unsubstituted aromatic hydrocarbon group having 6 to 30 ring atoms, a dibenzofuranyl group or a dibenzo groupThienyl (debenzothiophenyl group) substituted aromatic hydrocarbon groups containing 6 to 30 ring atoms, unsubstituted dibenzofuranyl or unsubstituted dibenzothienyl.

From R ¹ And R is ² The aromatic hydrocarbon group having 6 to 30 ring atoms, which is represented by the heteroaryl group having 3 to 30 ring atoms, is preferably represented by the following formula:

(HAr) _a ―Z―** (i)

wherein the method comprises the steps of

* Represents a bonding site;

z represents an unsubstituted or substituted divalent aromatic hydrocarbon group;

a represents 1, 2 or 3;

HAr is represented by:

wherein the method comprises the steps of

X represents an oxygen atom or a sulfur atom.

Selected from R ¹⁴ To R ²¹ Is a single bond to Z.

R is not a single bond to Z ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ 、R ¹⁹ 、R ²⁰ And R is ²¹ Represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms or an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms.

Selected from R ¹⁴ To R ²¹ Each independently of the others may bond to each other to form a substituted or unsubstituted cyclic structure, or may not bond to each other and thus may not form a cyclic structure.

R ¹ And R is ² Each is preferably a substituted or unsubstituted group selected from the following formulae.

Wherein any group is omitted and the dotted line is the bonding site.

R ¹ And R is ² More preferably each is a substituted or unsubstituted group selected from the following formulas.

Wherein any group is omitted and the dotted line is the bonding site.

X ¹ Represents N or CR ¹¹ ；

X ² Represents N or CR ¹² ；

X ³ Represents N or CR ¹³ ；

Wherein X is ¹ 、X ² And X ³ At least one, preferably at least two, of which is N. Most preferably, X ¹ 、X ² And X ³ Is N.

R ¹¹ 、R ¹² And R is ¹³ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms; preferably R ¹¹ 、R ¹² And R is ¹³ Each independently represents hydrogen, unsubstituted or substituted phenyl, unsubstituted or substituted pyridyl, unsubstituted or substituted alkyl having 1 to 4 carbon atoms, or unsubstituted or substituted cycloalkyl having 5 to 6 ring carbon atoms; more preferably hydrogen, unsubstituted phenyl, unsubstituted pyridyl or unsubstituted alkyl having 1 to 4 carbon atoms;

or alternatively

R ¹ And R is ¹¹ And/or R ¹² The method comprises the steps of carrying out a first treatment on the surface of the And/or R ² And R is ^-11 And/or R ¹³ May together form a substituted or unsubstituted carbocyclic or heterocyclic ring, preferably a 5 or 6 membered substituted or unsubstituted carbocyclic or heterocyclic ring.

Most preferably, R ¹¹ 、R ¹² And R is ¹³ Is hydrogen, unsubstitutedPhenyl, unsubstituted pyridinyl or unsubstituted alkyl having 1 to 4 carbon atoms, even most preferably R ¹¹ 、R ¹² And R is ¹³ Is hydrogen.

R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 30 ring atoms, an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 18 ring carbon atoms, or CN; preferably R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ Each independently represents hydrogen, unsubstituted or substituted phenyl, unsubstituted or substituted pyridyl, unsubstituted or substituted alkyl having 1 to 4 carbon atoms, or unsubstituted or substituted cycloalkyl having 5 to 6 ring carbon atoms; more preferably hydrogen, unsubstituted phenyl, unsubstituted pyridyl or unsubstituted alkyl having 1 to 4 carbon atoms;

or alternatively

wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of which is a bonding site.

Most preferably, R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ Is hydrogen, unsubstituted phenyl, unsubstituted pyridyl or unsubstituted alkyl having 1 to 4 carbon atoms, even most preferably R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ Is hydrogen, wherein R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of which is a bonding site.

In the compounds of formula (I), L represents an unsubstituted or substituted divalent aromatic hydrocarbon group containing 6 to 30 ring atoms, an unsubstituted or substituted divalent heteroaryl group containing 3 to 30 ring atoms; preferably, L represents an unsubstituted or substituted divalent aromatic hydrocarbon group containing 6 to 24 ring atoms, preferably 6 to 18 ring atoms, or an unsubstituted or substituted divalent heteroaryl group containing 3 to 24 ring atoms, preferably 3 to 18 ring atoms; more preferably, L represents an unsubstituted or substituted divalent phenyl group, an unsubstituted or substituted divalent naphthyl group, an unsubstituted or substituted divalent anthryl group, an unsubstituted or substituted phenanthryl group, an unsubstituted or substituted triphenylene group, a 9, 9-dimethylfluorenyl group, an unsubstituted or substituted 9, 9-diphenylfluorenyl group, or an unsubstituted or substituted divalent heteroaryl group containing 3 to 24 ring atoms, preferably 3 to 14 ring atoms; most preferred are unsubstituted 1, 4-phenylene, unsubstituted 1, 3-phenylene, 1, 4-phenylene substituted with phenyl, naphthyl or phenanthryl, 1, 3-phenylene substituted with phenyl, naphthyl or phenanthryl, unsubstituted 1, 4-naphthylene, unsubstituted 1, 5-naphthylene, unsubstituted 1, 6-naphthylene, unsubstituted 2,7-9, 9-diphenyl-fluorene, unsubstituted 2,5-9, 9-diphenyl-fluorene, unsubstituted 2,7-9, 9-dimethyl-fluorene, unsubstituted 2,5-9, 9-dimethyl-fluorene, unsubstituted 2, 7-triphenylene, unsubstituted 9, 10-anthracenyl, substituted 9, 6-anthracenyl, substituted 9, 7-anthracenyl or unsubstituted divalent heteroaryl groups containing from 3 to 24 ring atoms, preferably from 3 to 14 ring atoms.

Group- (L) _m -preferably represented by:

/>

wherein the dashed line is the bonding site.

Examples of compounds of formula (I) are given below:

/>

synthesis of Compound of formula (I)

The compounds of formula (I) may be prepared, for example, by the following methods:

i) Preparation of intermediate B

Wherein the method comprises the steps of

Q is an unsubstituted alkyl group having 1 to 8 carbon atoms, an unsubstituted cycloalkyl group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms substituted by one or two unsubstituted alkyl groups having 1 to 8 carbon atoms, an unsubstituted alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, wherein two alkyl groups Q or two alkoxy groups Q together may form a five-or six-membered substituted or unsubstituted ring,

hal is a halide, preferably selected from the group consisting of I, F, cl and Br, or a pseudohalide, preferably selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, toluenesulfonate and nonafluoromethanesulfonate.

All other residues, groups and indices are defined above.

Intermediate a is typically prepared from the corresponding halide in the presence of a borating agent:

suitable borating agents are boric acid or boric acid esters, such as alkyl borates, alkenyl borates, alkynyl borates and aryl borates. Preferred borating agents have the general formula Q ₂ BH or Q ₂ B-BQ ₂ Wherein Q is as defined above. For example, pinacolborane (Hbpin), bis (pinacolato) diborane (B) ₂ Pin ₂ ) And bis (catechol) diborane (B) ₂ Cat ₂ ). Other suitable borating agents are dioxaboroles, such as 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaboroles.

The boration reaction may be carried out in the presence or absence of a catalyst.

In the case of the boronation being carried out in the absence of a catalyst, the halide is treated, for example, with an organolithium reagent, followed by the boronation with a boronating agent. Suitable borating agents are mentioned above.

In the case where the boronation is carried out in the presence of a catalyst, the preferred catalyst is a Pd catalyst. Suitable Pd catalysts are, for example, those havingPd (0) complexes of bidentate ligands such as dba (dibenzylideneacetone), or Pd (II) salts such as PdCl ₂ Or Pd (OAc) ₂ With bidentate phosphine ligands such as dppf ((diphenylphosphino) ferrocene), dppp ((diphenylphosphino) propane), BINAP (2, 2 '-bis (diphenylphosphino) -1,1' -binaphthyl), xantphos (4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene), DPEphos (bis [ (2-diphenylphosphino) phenyl)]Ether) or Josiphos, or with monodentate phosphine ligands such as triphenylphosphine, tri-o-tolylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl (XPhos) or N-heterocyclic carbenes such as 1, 3-bis (2, 6-diisopropylphenyl) imidazol-2-ylidene (IPr), 1, 3-dimethylimidazol-2-ylidene (Imes).

Wherein R and R' are typically substituted or unsubstituted phenyl groups.

ii) preparation of the compound of formula (I)

Wherein the method comprises the steps of

Residues R forming the bonding site in the compound of formula (I) ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of them is Hal',

hal' is a halide, preferably selected from the group consisting of I, F, cl and Br, or a pseudohalide, preferably selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, toluenesulfonate and nonafluoromethanesulfonate.

All other residues, groups and indices are defined above.

The method of preparation of the compound of formula (I) according to the present invention is not particularly limited and it is prepared according to known methods, for example by Suzuki coupling as described in Journal of American Chemistry Society,1999,121,9550-9561 or Chemical Reviews,1995,95,2457-2483 or Kumada coupling as described in org.

Preparation of intermediate a (illustrated for m=2)

Wherein the method comprises the steps of

Q' is unsubstituted alkyl having 1 to 8 carbon atoms, unsubstituted cycloalkyl having 3 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms substituted by one or two unsubstituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkoxy having 1 to 8 carbon atoms, hydroxy, wherein two alkyl groups Q or two alkoxy groups Q together may form a five-or six-membered substituted or unsubstituted ring,

Hal "and Hal'" each independently represent a halide, preferably selected from the group consisting of I, F, cl and Br, or a pseudohalide, preferably selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, toluenesulfonate and nonafluoromethanesulfonate.

All other residues, groups and indices are defined above.

The preparation of intermediate a is generally the same as mentioned above for the preparation of the compound of formula (I).

Preparation of intermediate C (for y=nr ¹⁰ Exemplary embodiments of the invention

i)R ³ And R is ¹⁰ Identical to

Or alternatively

Wherein the method comprises the steps of

R is defined as R ³ And R is ¹⁰ The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

Hal "" means a halide, preferably selected from the group consisting of I, F, cl and Br, or a pseudohalide, preferably selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, toluenesulfonate and nonafluoromethanesulfonate.

All other residues, groups and indices are defined above.

Suitable bases and reaction conditions are known to those skilled in the art. Examples of suitable bases are potassium carbonate, sodium hydride, lithium diisopropylamide or triethylamine.

ii)R ³ And R is ¹⁰ Different from

iia)

iib)

iic)

Wherein the method comprises the steps of

Hal ""' denotes a halide, preferably selected from the group consisting of I, F, cl and Br, or a pseudohalide, preferably selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, toluenesulfonate and nonafluoromethanesulfonate.

All other residues, groups and indices are defined above.

Details of all reaction steps and process conditions are mentioned in the examples of the present application.

The compounds of formula (I) have been found to be particularly suitable for use in applications where carrier conductivity is required, in particular for use in organic electronics applications, such as switching elements selected from organic transistors, for example organic FETs and organic TFTs, organic solar cells and Organic Light Emitting Diodes (OLEDs).

In the present application, the term organic EL device (organic electroluminescent device) is used interchangeably with the term Organic Light Emitting Diode (OLED); that is, these two terms have the same meaning in the sense of the present application.

The invention also relates to a material for an organic EL device comprising at least one compound of formula (I).

The organic transistor generally includes: a semiconductor layer formed of an organic layer having a charge transport capability; a gate electrode formed of a conductive layer; and an insulating layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are sequentially mounted on such a device to thereby manufacture a transistor element. In addition, other layers known to those skilled in the art may also be present in the organic transistor. The layer having charge transport capability may comprise a compound of formula (I).

An organic solar cell (photoelectric conversion element) generally includes an organic layer existing between two plate-type electrodes arranged in parallel. The organic layer may be disposed on the comb-shaped electrode. There is no particular limitation on the position of the organic layer, and there is no particular limitation on the material of the electrode. However, when plate-type electrodes arranged in parallel are used, at least one electrode is preferably formed of a transparent electrode such as an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed of two sublayers, i.e., a layer having p-type semiconductor characteristics or hole transport capability and a layer having n-type semiconductor characteristics or charge transport capability. In addition, other layers known to those skilled in the art may be present in the organic solar cell. The layer having charge transport capability may comprise a compound of formula (I).

The compounds of the formula (I) are particularly suitable for use as charge and/or exciton blocking materials, i.e. as hole/exciton blocking materials, and/or charge transport materials, i.e. hole transport materials or electron transport materials, preferably as electron transport materials and/or hole blocking materials, in OLEDs.

In the case of using the compounds of the formula (I) according to the invention for OLEDs, OLEDs having good overall properties, preferably long life, high efficiency and/or low driving voltage, are obtained.

Organic electroluminescent device

According to one aspect of the present invention there is provided a material for an organic electroluminescent device comprising at least one compound of formula (I).

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising at least one compound of formula (I). The organic electroluminescent device generally includes: a cathode, an anode, and one or more organic thin film layers comprising an emissive layer disposed between the cathode and the anode, wherein at least one of the organic thin film layers comprises at least one compound of formula (I).

In this specification, with respect to "one or more organic thin film layers disposed between a cathode and an anode", if there is only one organic layer between the cathode and the anode, it means the layer, and if there are a plurality of organic layers between the cathode and the anode, it means at least one layer thereof.

According to another aspect of the present invention there is provided the use of a non-compound of formula (I) according to the present invention in an organic electroluminescent device.

In one embodiment, the organic EL device has a hole transport layer between the anode and the emissive layer.

In one embodiment, the organic EL device has an electron transport layer between the cathode and the emissive layer.

In one embodiment, the organic EL device has a hole blocking layer between the electron transport layer and the emissive layer.

One or more layers between the emissive layer and the anode:

in the organic EL device according to the present invention, one or more organic thin film layers may be present between the emission layer and the anode. If there is only one organic layer between the emission layer and the anode, it refers to that layer, and if there are a plurality of organic layers, it refers to at least one layer thereof. For example, if there are two or more organic layers between the emission layer and the anode, the organic layer closer to the emission layer is referred to as a "hole transport layer", and the organic layer closer to the anode is referred to as a "hole injection layer". Each of the "hole transport layer" and the "hole injection layer" may be a single layer, or may be formed of two or more layers. One of these layers may be a single layer, and the other may be formed of two or more layers.

One or more layers between the emissive layer and the cathode:

similarly, in the organic EL device according to the present invention, one or more organic thin film layers (electron transport region including at least an electron transport layer and preferably also an electron injection layer and/or a hole blocking layer) may be present between the emission layer and the cathode. If there is only one organic layer between the emissive layer and the cathode, it refers to that layer, and if there are multiple organic layers, it refers to at least one of them. For example, if there are two or more organic layers between the emission layer and the cathode, the organic layer closest to the emission layer is referred to as a "hole blocking layer", the organic layer closest to the "hole blocking layer" is referred to as an "electron transport layer", and the organic layer closer to the cathode is referred to as an "electron injection layer". Each of the "hole blocking layer", "electron transporting layer", and "electron injecting layer" may be a single layer, or may be formed of two or more layers. One of these layers may be a single layer, and the other may be formed of two or more layers.

The one or more organic thin film layers, preferably the "electron transport region", between the emissive layer and the cathode preferably comprise a compound represented by formula (I).

Thus, in a preferred embodiment, the organic thin film layer of the organic electroluminescent device comprises an electron transport region disposed between the emissive layer and the cathode, wherein the electron transport region comprises at least one compound represented by formula (I). The compound represented by formula (I) preferably acts as a "hole blocking" material in the hole blocking layer and/or as an "electron transporting" material in the electron transporting layer.

In one exemplary embodiment, one or more organic thin film layers of the organic EL device of the present invention include at least an emission layer and an electron transport region. The electron transport region is disposed between the emissive layer and the cathode and includes at least an electron transport layer, and preferably also an electron injection layer and/or a hole blocking layer. The electron transport region may include an electron injection layer and an electron transport layer, and may further include a hole blocking layer and an optional spacer layer. In addition to the above-described layers, one or more organic thin film layers may be provided by layers applied in known organic EL devices such as a hole injection layer, a hole transport layer, and an electron blocking layer. The one or more organic thin film layers may comprise an inorganic compound.

A layer configuration of an organic EL device according to an aspect of the present invention will be explained.

An organic EL device according to an aspect of the present invention includes a cathode, an anode, and one or more organic thin film layers including an emission layer disposed between the cathode and the anode. The organic layer includes at least one layer composed of an organic compound. Alternatively, the organic layer is formed by laminating a plurality of layers composed of an organic compound. The organic layer may contain an inorganic compound in addition to the organic compound.

At least one of the organic layers is an emissive layer. The organic layer may be constituted of, for example, a single emission layer, or may include other layers that may be employed in the layer structure of the organic EL device. The layer that can be employed in the layer structure of the organic EL device is not particularly limited, but examples thereof include a hole transport region (hole transport layer, hole injection layer, electron blocking layer, exciton blocking layer, etc.), an emission layer, a spacer layer, and an electron transport region (electron transport layer, electron injection layer, hole blocking layer, etc.) disposed between the cathode and the emission layer.

The organic EL device according to an aspect of the present invention may be, for example, a fluorescent or phosphorescent single-color light emitting device or a fluorescent/phosphorescent hybrid white light emitting device.

Furthermore, it may be a simple type device having a single transmitting unit or a serial type device having a plurality of transmitting units.

An "emission unit" in this specification is a minimum unit including organic layers, wherein at least one of the organic layers is an emission layer, and light is emitted by recombination of injected holes and electrons.

In addition, the emission layer described in this specification is an organic layer having an emission function. The emission layer is, for example, a phosphorescent emission layer, a fluorescent emission layer, or the like, and may be a single layer, or a laminate of a plurality of layers.

The "emission unit" may be a stacked unit having a plurality of phosphorescent emission layers and/or fluorescent emission layers. In this case, for example, a spacer layer for preventing excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer may be disposed between the respective emitting layers.

As a simple type organic EL device, a device configuration such as anode/emission unit/cathode can be given.

An example of a representative layer structure of the transmitting unit is shown below. The layers in brackets are arbitrarily provided:

(a) (hole injection layer /) hole transport layer/fluorescent emission layer (/ electron transport layer/electron injection layer)

(b) (hole injection layer /) hole transport layer/phosphorescent light emitting layer (/ electron transport layer/electron injection layer)

(c) (hole injection layer /) hole transport layer/first fluorescent emission layer/second fluorescent emission layer (/ electron transport layer/electron injection layer)

(d) (hole injection layer /) hole transport layer/first phosphor layer/second phosphor layer (/ electron transport layer/electron injection layer)

(e) (hole injection layer /) hole transport layer/phosphorescent emitter layer/spacer layer/fluorescent emitter layer (/ electron transport layer/electron injection layer)

(f) (hole injection layer /) hole transport layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/spacer layer/fluorescent light emitting layer (/ electron transport layer/electron injection layer)

(g) (hole injection layer /) hole transport layer/first phosphor layer/spacer layer/second phosphor emission layer/spacer layer/fluorescence emission layer (/ electron transport layer/electron injection layer)

(h) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/spacer layer/first fluorescent light emitting layer/second fluorescent light emitting layer (/ electron transport layer/electron injection layer)

(i) (hole injection layer /) hole transport layer/electron blocking layer/fluorescent emission layer (/ electron transport layer/electron injection layer)

(j) (hole injection layer /) hole transport layer/electron blocking layer/phosphorescent light emitting layer (/ electron transport layer/electron injection layer)

(k) (hole injection layer /) hole transport layer/exciton blocking layer/fluorescent emission layer (/ electron transport layer/electron injection layer)

(l) (hole injection layer /) hole transport layer/exciton blocking layer/phosphorescent light emitting layer (/ electron transport layer/electron injection layer)

(m) (hole injection layer /) first hole transport layer/second hole transport layer/fluorescent emission layer (/ electron transport layer/electron injection layer)

(n) (hole injection layer /) first hole transport layer/second hole transport layer/fluorescent emission layer (/ first electron transport layer/second electron transport layer/electron injection layer)

(o) (hole injection layer /) first hole transport layer/second hole transport layer/phosphorescent light emitting layer (/ electron transport layer/electron injection layer)

(p) (hole injection layer /) first hole transport layer/second hole transport layer/phosphorescent light emitting layer (/ first electron transport layer/second electron transport layer/electron injection layer)

(q) (hole injection layer /) hole transport layer/fluorescent emission layer/hole blocking layer (/ electron transport layer/electron injection layer)

(r) (hole injection layer /) hole transport layer/phosphorescent light emitting layer/hole blocking layer (/ electron transport layer/electron injection layer)

(s) (hole injection layer /) hole transport layer/fluorescent emission layer/exciton blocking layer (/ electron transport layer/electron injection layer)

(t) (hole injection layer /) hole transport layer/phosphorescent emissive layer/exciton blocking layer (/ electron transport layer/electron injection layer)

The layer structure of the organic EL device according to an aspect of the present invention is not limited to the above-mentioned examples.

For example, when the organic EL device has a hole injection layer and a hole transport layer, it is preferable that the hole injection layer is provided between the hole transport layer and the anode. Further, when the organic EL device has an electron injection layer and an electron transport layer, it is preferable that the electron injection layer is disposed between the electron transport layer and the cathode. In addition, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be formed of a single layer or formed of a plurality of layers.

The plurality of phosphorescent light emitting layers and/or the fluorescent light emitting layer may be light emitting layers that emit mutually different colors. For example, the emission unit (f) may include a hole transport layer/a first phosphorescent layer (red light emission)/a second phosphorescent emission layer (green light emission)/a spacer layer/a fluorescent emission layer (blue light emission)/an electron transport layer.

An electron blocking layer may be disposed between each light emitting layer and the hole transport layer or the spacer layer. In addition, a hole blocking layer may be disposed between each of the emission layers and the electron transport layer. By providing an electron blocking layer or a hole blocking layer, electrons or holes can be confined in the emission layer, thereby improving the recombination probability of carriers in the emission layer and improving the light emission efficiency.

As a representative device configuration of the tandem-type organic EL device, for example, a device configuration such as anode/first emission unit/intermediate layer/second emission unit/cathode may be given:

the first transmitting unit and the second transmitting unit are for example independently selected from the transmitting units mentioned above.

The intermediate layer is also commonly referred to as an intermediate electrode, intermediate conductive layer, charge generation layer, electron withdrawing layer, connection layer, connector layer, or intermediate insulating layer. The intermediate layer is a layer that supplies electrons to the first emission unit and holes to the second emission unit, and may be formed of a known material.

Fig. 1 shows a schematic configuration of one example of an organic EL device of the present invention. The organic EL device 1 includes a substrate 2, an anode 3, a cathode 4, and an emission unit 10 disposed between the anode 3 and the cathode 4. The emissive unit 10 comprises an emissive layer 5 preferably comprising a host material and a dopant. A hole injection and transport layer 6 or the like may be provided between the emission layer 5 and the anode 3, and an electron injection layer 9 and an electron transport layer 8 and/or a hole blocking layer 7 or the like (electron transport region 11) may be provided between the emission layer 5 and the cathode 4. An electron blocking layer may be provided on the anode 3 side of the emissive layer 5. Due to such a configuration, electrons or holes can be confined within the emission layer 5, whereby the possibility of generating excitons in the emission layer 5 can be improved.

Hereinafter, functions, materials, and the like of the respective layers constituting the organic EL device described in the present specification will be explained.

(substrate)

The substrate serves as a support for the organic EL device. The substrate preferably has a light transmittance of 50% or more in the visible light region of 400 to 700nm in wavelength, and a smooth substrate is preferable. Examples of the material of the substrate include glass such as soda lime glass, aluminosilicate glass, quartz glass, plastic, and the like. As the substrate, a flexible substrate can be used. The flexible substrate refers to a substrate that can be bent (flexible), and examples thereof include a plastic substrate and the like. Specific examples of the material for forming the plastic substrate include polycarbonate, polyacrylate (polyacrylate), polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, polyethylene naphthalate, and the like. In addition, an inorganic vapor deposition film may be used.

(anode)

As the anode, for example, a metal, an alloy, a conductive compound, a mixture thereof, or the like is preferably used and has a high work function (specifically, 4.0eV or more). Specific examples of the material of the anode include indium oxide-tin oxide (ITO: indium tin oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide or zinc oxide, graphene, and the like. In addition, gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (e.g., titanium oxide) may also be used.

The anode is typically formed by depositing these materials onto a substrate by sputtering. For example, indium oxide-zinc oxide can be formed by a sputtering method by using a target in which 1 to 10 mass% of zinc oxide is added relative to indium oxide. Further, indium oxide containing tungsten oxide or zinc oxide can be formed by a sputtering method by using a target in which 0.5 to 5 mass% of tungsten oxide or 0.1 to 1 mass% of zinc oxide is added to indium oxide.

As other methods for forming the anode, a vacuum deposition method, a coating method, an inkjet method, a spin coating method, or the like can be given. When silver paste or the like is used, a coating method, an inkjet method, or the like may be used.

The hole injection layer formed in contact with the anode is formed by using a material that allows easy hole injection regardless of the work function of the anode. For this reason, in the anode, common electrode materials such as metals, alloys, conductive compounds, and mixtures thereof may be used. Specifically, materials having a small work function such as alkali metals, e.g., lithium and cesium; alkaline earth metals such as calcium and strontium; alloys containing these metals (e.g., magnesium-silver alloys and aluminum-lithium alloys); rare earth metals such as europium and ytterbium; alloys containing rare earth metals.

(hole transporting layer)/(hole injecting layer/electron blocking layer)

The hole transport layer is an organic layer formed between the emission layer and the anode, and has a function of transporting holes from the anode to the emission layer. If the hole transport layer is made up of multiple layers, the organic layer closer to the anode may be generally defined as a hole injection layer. The hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit. The hole injection layer is typically used to stabilize hole injection from the anode to a hole transport layer, which is typically composed of an organic material. An organic material having good contact with the anode or an organic material having p-type doping is preferably used for the hole injection layer.

p-doping typically consists of one or more p-dopant materials and one or more host materials. The host material preferably has a shallower HOMO level, and the p-dopant preferably has a deeper LUMO level to enhance the carrier density of the layer. Aryl or heteroaryl amine compounds are preferably used as matrix materials. Specific examples for the matrix material are the same as those for the hole transport layer explained in the latter part. Specific embodiment for p-dopants Examples are the acceptor materials mentioned below, preferably quinone compounds having one or more electron withdrawing groups, such as F ₄ TCNQ, 1,2, 3-tris [ (cyano) (4-cyano-2, 3,5, 6-tetrafluorophenyl) methylene]And (3) cyclopropane.

As the p-type dopant material for the hole injection layer, an acceptor material having high planarity or a condensed aromatic hydrocarbon material or a condensed heterocyclic ring is preferably used.

Specific examples for acceptor materials are quinone compounds with one or more electron withdrawing groups, e.g.F ₄ TCNQ (2, 3,5, 6-tetrafluoro-7, 8-tetracyanoquinodimethane) and 1,2, 3-tris [ (cyano) (4-cyano-2, 3,5, 6-tetrafluorophenyl) methylene]Cyclopropane; hexa-azatriphenylene compounds having one or more electron withdrawing groups, such as hexa-azatriphenylene-hexanitrile; an aromatic hydrocarbon compound having one or more electron withdrawing groups; and aryl boron compounds having one or more electron withdrawing groups.

The ratio of the p-type dopant is preferably less than 20% by mole, more preferably less than 10%, such as 1%, 3% or 5% relative to the matrix material.

The hole transport layer is generally used for efficiently injecting and transporting holes, and aromatic or heterocyclic amine compounds are preferably used.

Specific examples of the compound for a hole transport layer are represented by the general formula (H),

Wherein the method comprises the steps of

Ar ₁ To Ar ₃ Each independently represents a substituted or unsubstituted aryl group having 5 to 50 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, spirobifluorenyl, indenofluorenyl, carbazolyl, dibenzofuranyl, dibenzothienyl, carbazole-substituted aryl, dibenzofuran-substituted aryl or dibenzothiophene-substituted aryl; selected from Ar ¹ To Ar ³ May have two or more substituentsTo bond to each other to form a ring structure such as a carbazole ring structure or an acridine (acridane) ring structure.

Preferably Ar ₁ To Ar ₃ Having an additional aryl or heterocyclic amine substituent, more preferably Ar ₁ Having additional arylamino substituents, in which case Ar is preferred ₁ Represents a substituted or unsubstituted biphenylene group or a substituted or unsubstituted fluorenylene group.

A second hole transport layer is preferably interposed between the first hole transport layer and the emissive layer to enhance device performance by blocking excess electrons or excitons. Specific examples for the second hole transport layer are the same as those for the first hole transport layer. Preferably, the second hole transport layer has a higher triplet energy to block triplet excitons, such as a dicarbazole compound, a benzidine compound, a triphenylamine compound, a fluorenyl amine compound, a carbazole-substituted aryl amine compound, a dibenzofuran-substituted aryl amine compound, and a dibenzothiophene-substituted aryl amine compound.

This second hole transport layer (also referred to as an electron blocking layer) disposed adjacent to the emission layer has a function of preventing electrons from leaking from the emission layer to the hole transport layer.

(emissive layer)

The emission layer is a layer containing a substance having high light-emitting properties (a light-emitting material or a dopant material). As the dopant material, various materials can be used. For example, a fluorescent emission compound (fluorescent dopant), a phosphorescent emission compound (phosphorescent dopant), or the like may be used. The fluorescent emission compound is a compound capable of emitting light from a singlet excited state, and an emission layer containing the fluorescent emission compound is referred to as a fluorescent emission layer. Further, the phosphorescent emissive compound is a compound capable of emitting light from a triplet excited state, and an emission layer containing the phosphorescent emissive compound is referred to as a phosphorescent emissive layer.

The emissive layer preferably comprises at least one dopant material and at least one host material that allows it to efficiently emit light. In some documents, the dopant material is referred to as a guest material, an emitter, or an emissive material. In some documents, the host material is referred to as a matrix material.

A single emissive layer may comprise multiple dopant materials and multiple host materials. Furthermore, there may be multiple emissive layers.

In this specification, a host material combined with a fluorescent dopant is referred to as a "fluorescent host", and a host material combined with a phosphorescent dopant is referred to as a "phosphorescent host". It is noted that fluorescent and phosphorescent hosts are not classified by molecular structure alone. The phosphorescent host is a material for forming a phosphorescent light emitting layer containing a phosphorescent dopant, but does not mean that it cannot be used as a material for forming a fluorescent light emitting layer. The same applies to fluorescent hosts.

The content of the dopant material in the host in the emission layer is generally not particularly limited. The concentration of each of the phosphorescent or fluorescent dopants typically present in a suitable host is generally known to those skilled in the art. With respect to sufficient emission and concentration quenching, the content is preferably 0.5 to 70 mass%, more preferably 0.8 to 30 mass%, further preferably 1 to 30 mass%, still further preferably 1 to 20 mass%. The remaining mass of the emissive layer is typically provided by one or more host materials.

(fluorescent dopant)

Suitable fluorescent dopants are generally known to those skilled in the art. As the fluorescent dopant, for example, a condensed polycyclic aromatic compound, a styrylamine compound, a condensed cyclic amine compound, a boron-containing compound, a pyrrole compound, an indole compound, a carbazole compound can be given. Among these, a condensed cyclic amine compound, a boron-containing compound, and a carbazole compound are preferable.

As the condensed cyclic amine compound, a diaminopyrene compound, a diamino compound can be givenCompounds, diaminoanthracene compounds, diaminofluorene compounds fused to one or more benzofuran backbones, and the like.

As the boron-containing compound, a pyrrolomethylene compound, a triphenylborane compound, and the like can be given.

(phosphorescent dopant)

Suitable phosphorescent dopants are generally known to those skilled in the art. As phosphorescent dopants, for example, phosphorescent light-emitting heavy metal complexes and phosphorescent light-emitting rare earth metal complexes can be given.

As the heavy metal complex, iridium complex, osmium complex, platinum complex, and the like can be given. The heavy metal complexes are, for example, ortho-metalated complexes of metals selected from iridium, osmium and platinum.

Examples of rare earth metal complexes include terbium complexes, europium complexes, and the like. Specifically, tris (acetylacetonate) (Shan Feige in) terbium (III) (abbreviation Tb (acac) ₃ (Phen)), tris (1, 3-diphenyl-1, 3-malonate) (Shan Feige in) europium (III) (abbreviation Eu (DBM) ₃ (Phen)), tris [1- (2-thenoyl) -3, 3-trifluoroacetone](Shan Feige) europium (III) (abbreviated Eu (TTA) ₃ (Phen)), and the like. These rare earth metal complexes are preferred as phosphorescent dopants because rare earth metal ions emit light due to electron transitions between different multiplexing.

As the blue phosphorescent dopant, for example, iridium complex, osmium complex, platinum complex, and the like can be given. In particular, bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2 'can be given']Iridium (III) tetrakis (1-pyrazolyl) borate (abbreviation: FIr 6), bis [2- (4 ',6' -difluorophenyl) pyridinyl-N, C2 ] ']Iridium (III) picolinate (abbreviation: ir (CF) ₃ ppy) ₂ (pic)), bis [2- (4 ',6' -difluorophenyl) pyridinyl-N, C2 ] ']Iridium (III) acetylacetonate (abbreviation: FIracac) and the like.

As the green phosphorescent dopant, for example, iridium complex and the like can be given. In particular, tris (2-phenylpyridyl-N, C2') iridium (III) (abbreviation: ir (ppy) ₃ ) Bis (1, 2-diphenyl-1H-benzimidazole) acetylacetonate iridium (III) (abbreviation: ir (pbi) ₂ (acac)), bis (benzo [ h)]Quinoline) iridium (III) acetylacetonate (abbreviation: ir (bzq) ₂ (acac)) and the like.

As the red phosphorescent dopant, iridium complex, platinum complex, terbium complex, europium complex, and the like can be given. In particular, bis [2- (2' -benzo [4, 5-alpha ] can be given]Thiophene (S)Group) pyridinyl-N, C3']Iridium (III) acetylacetonate (abbreviation: ir (btp)) ₂ (acac)), bis (1-phenylisoquinoline) -N, C2') iridium (III) acetylacetonate (abbreviation: ir (piq) ₂ (acac)), (acetylacetonato) bis [2, 3-bis (4-fluorophenyl) quinoxaline ]Iridium (III) (abbreviation: ir (Fdpq) ₂ (acac)), 2,3,7,8,12,13,17, 18-octaethyl-21 h,23 h-porphyrin platinum (II) (abbreviated PtOEP), and the like.

(Main Material)

As the host material, for example, metal complexes such as aluminum complex, beryllium complex, and zinc complex; heterocyclic compounds such as indole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinoline compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, oxadiazole compounds, benzimidazole compounds, phenanthroline compounds; condensed polyaromatic hydrocarbon (PAH) compounds such as naphthalene compounds, triphenylene compounds, carbazole compounds, anthracene compounds, phenanthrene compounds, pyrene compounds,A compound, a naphthacene compound, a fluoranthene compound; and aromatic amine compounds such as triarylamine compounds and fused polycyclic aromatic amine compounds. Multiple types of host materials may be used in combination.

As the fluorescent host, a compound having a higher singlet energy level than the fluorescent dopant is preferable. For example, heterocyclic compounds, condensed aromatic compounds, and the like can be given. As the condensed aromatic compound, an anthracene compound, a pyrene compound, Compounds, naphthacene compounds and the like are preferable. The anthracene compound preferentially acts as a blue fluorescent host.

As the phosphorescent host, a compound having a higher triplet energy level than the phosphorescent dopant is preferable. For example, metal complexes, heterocyclic compounds, condensed aromatic compounds, and the like can be given. Among these, indole compounds, carbazole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinolone compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, naphthalene compounds, triphenylene compounds, phenanthrene compounds, fluoranthene compounds, and the like can be given.

Preferred host materials are substituted or unsubstituted polyaromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds, preferably substituted or unsubstituted anthracene compounds or substituted or unsubstituted pyrene compounds, more preferably substituted or unsubstituted anthracene compounds, most preferably anthracene compounds represented by the following formula (10).

In formula (10), ar ³¹ And Ar is a group ³² Each independently represents a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a heterocyclic group having 5 to 50 ring atoms.

R ⁸¹ To R ⁸⁸ Each independently represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring carbon atoms, a substituted or unsubstituted arylthio group having 6 to 50 ring carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group.

In formula (10):

aryl groups having 6 to 50 ring carbon atoms are preferably aryl groups having 6 to 40 ring carbon atoms, more preferably aryl groups having 6 to 30 ring carbon atoms.

The heterocyclic group having 5 to 50 ring atoms is preferably a heterocyclic group having 5 to 40 ring atoms, more preferably a heterocyclic group having 5 to 30 ring atoms. More preferably, the heterocyclyl is a substituted or unsubstituted heteroaryl having 5 to 30 ring atoms. Suitable substituted or unsubstituted heteroaryl groups are mentioned above.

The alkyl group having 1 to 50 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms.

The alkoxy group having 1 to 50 carbon atoms is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and still more preferably an alkoxy group having 1 to 5 carbon atoms.

The aralkyl group having 7 to 50 carbon atoms is preferably an aralkyl group having 7 to 30 carbon atoms, more preferably an aralkyl group having 7 to 20 carbon atoms.

The aryloxy group having 6 to 50 ring carbon atoms is preferably an aryloxy group having 6 to 40 ring carbon atoms, more preferably an aryloxy group having 6 to 30 ring carbon atoms.

The arylthio group having 6 to 50 ring carbon atoms is preferably an arylthio group having 6 to 40 ring carbon atoms, more preferably an arylthio group having 6 to 30 ring carbon atoms.

The alkoxycarbonyl group having 2 to 50 carbon atoms is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, and still more preferably an alkoxycarbonyl group having 2 to 5 carbon atoms.

Examples of halogen atoms are fluorine atoms, chlorine atoms and bromine atoms.

Ar ³¹ And Ar is a group ³² Preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.

(electron transport region)/(electron transport layer/electron injection layer/hole blocking layer)

The electron transport region is an organic layer or organic layers formed between the emission layer and the cathode, and has a function of transporting electrons from the cathode to the emission layer. Thus, the electron transport region comprises at least one electron transport layer comprising an electron transport material. When the electron transport region is formed of a plurality of layers, the organic layer or the inorganic layer closer to the cathode is generally defined as an electron injection layer (see, for example, fig. 1, in which the electron injection layer 9, the electron transport layer, and preferably the hole blocking layer 7 form an electron transport region 11). The electron injection layer has a function of efficiently injecting electrons from the cathode to the organic layer unit. Preferred electron injecting materials are alkali metals, alkali metal compounds, alkali metal complexes, alkaline earth metals, metal complexes and compounds, and rare earth metals or rare earth metal complexes and compounds. Suitable rare earth metals and rare earth metal compounds and complexes are mentioned below. Ytterbium is most preferred. In one embodiment of the invention, the electron injection layer does not comprise lithium quinolinate (lithium quinolate), preferably the electron injection layer does not comprise an alkali metal complex or compound. In the embodiment, the electron injection layer is preferably a rare earth metal, more preferably Yb. In another embodiment, the electron injection layer comprises an alkali metal compound or an alkali metal complex, preferably LiF or lithium quinolinate, preferably the electron injection layer is an alkali metal compound or an alkali metal complex, preferably LiF or lithium quinolinate. In a further embodiment, the electron transport material is doped with an alkali metal complex, preferably lithium quinolinate.

According to one embodiment, it is therefore preferred that the electron transport region comprises, in addition to the electron transport layer, one or more layers such as an electron injection layer (to enhance the efficiency and lifetime of the device), a hole blocking layer or an exciton/triplet blocking layer (layer 7 in fig. 1).

In a preferred embodiment of the present invention, the compounds of formula (I) are present in the electron transport region as electron transport materials, electron injection materials, hole blocking materials, exciton blocking materials and/or triplet blocking materials. More preferably, the compound of formula (I) is present in the electron transport region as an electron transport material and/or a hole blocking material.

According to one embodiment, it is preferred that an electron donating dopant is contained in the interface region between the cathode and the emissive unit. Due to such a configuration, the organic EL device can have increased brightness or long life. Here, the electron donating dopant means a dopant having a metal with a work function of 3.8eV or less. As specific examples thereof, at least one selected from alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earth metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and the like can be given.

As the alkali metal, li (work function: 2.9 eV), na (work function: 2.36 eV), K (work function: 2.28 eV), rb (work function: 2.16 eV), cs (work function: 1.95 eV) and the like can be given. Alkali metals having a work function of 2.9eV or less are particularly preferred. Among them, K, rb and Cs are preferable. Rb or Cs are further preferred. Cs is most preferred. As the alkaline earth metal, ca (work function: 2.9 eV), sr (work function: 2.0eV to 2.5 eV), ba (work function: 2.52 eV), mg (work function: 3.68 eV), and the like can be given. Alkaline earth metals having a work function of 2.9eV or less are particularly preferred. As the rare earth metal, sc, Y, ce, tb, yb and the like can be given. Rare earth metals having a work function of 2.9eV or less are particularly preferred.

Examples of the alkali metal compound include alkali metal chalcogenides such as Li ₂ O、Na ₂ O、Cs ₂ O、K ₂ O、Na ₂ S or Na ₂ Se, and alkali halides such as LiF, naF, csF, KF, liCl, KCl and NaCl. Among them, liF, li ₂ O and NaF are preferred. Examples of alkaline earth metal compounds include BaO, srO, caO, beO, baS, caSe and mixtures thereof, such as Ba _x Sr _1-x O(0<x<1) And Ba (beta) _x Ca _1-x O(0<x<1). Alkaline earth metal halides are, for example, fluorides, such as CaF ₂ 、BaF ₂ 、SrF ₂ 、MgF ₂ And BeF ₂ . Among them, baO, srO and CaO are preferable. Examples of the rare earth metal compound include one or more oxides, nitrides, oxynitrides or halides containing at least one element selected from Yb, sc, Y, ce, gd, tb and the like, particularly fluorides, such as YbF ₃ 、ScF ₃ 、ScO ₃ 、Y ₂ O ₃ 、Ce ₂ O ₃ 、GdF ₃ And TbF ₃ . Among these, ybF ₃ 、ScF ₃ And TbF ₃ Is preferred. Other suitable dopants are Al, ga, in,Cd. One or more oxides, nitrides and oxynitrides of Si, ta, sb and Zn, and nitrides and oxynitrides of Ba, ca, sr, yb, li, na and Mg.

The alkali metal complex, alkaline earth metal complex and rare earth metal complex are not particularly limited as long as they contain at least one of alkali metal ion, alkaline earth metal ion and rare earth metal ion as a metal ion. Meanwhile, preferred examples of the ligand include, but are not limited to, quinolinols, benzoquinolinols, acridinitriles, phenanthridinols, hydroxyphenyloxazoles, hydroxyphenylthiazoles, hydroxydiaryloxadiazoles, hydroxydiarylthiodiazoles, hydroxyphenylpyridines, hydroxyphenylbenzimidazoles, hydroxybenzotriazoles, hydroxyfluoroboranes, bipyridines, phenanthrolines, phthalocyanines, porphyrins, cyclopentadienes, β -diketones, and azomethines.

Regarding the form of addition of the electron donating dopant, it is preferable that the electron donating dopant is formed in the shape of a layer or island in the interface region. A preferred method for this formation is a method in which an organic compound (light emitting material or electron injecting material) for forming an interface region is simultaneously deposited in the case of depositing an electron donating dopant by a resistance heating deposition method, whereby the electron donating dopant is dispersed in the organic compound. In the case where the electron donating dopant is formed in a layer shape, a light emitting material or an electron injecting material serving as an organic layer in an interface is formed in a layer shape. Thereafter, the reducing dopant is separately deposited by a resistance heating deposition method to form a layer, which preferably has a thickness of 0.1nm to 15 nm. In the case where the electron donating dopant is formed in an island shape, a light emitting material or an electron injecting material serving as an organic layer in an interface is formed in the shape of an island. Thereafter, electron donating dopants are individually deposited by resistive heating deposition to form islands, which preferably have a thickness of 0.05nm to 1 nm.

As the electron-transporting material other than the compound of formula (I) used in the electron-transporting layer, an aromatic heterocyclic compound having one or more hetero atoms in the molecule can be preferably used. In particular, nitrogen-containing heterocyclic compounds are preferred.

According to one embodiment, it is preferred that the electron transport layer comprises a nitrogen-containing heterocyclic metal chelate.

According to another embodiment, it is preferred that the electron transport layer comprises a substituted or unsubstituted nitrogen-containing heterocyclic compound. Specific examples of preferred heterocyclic compounds for the electron transport layer are: a 6-membered azine compound; such as a pyridine compound, a pyrimidine compound, a triazine compound, a pyrazine compound, preferably a pyrimidine compound or a triazine compound; 6-membered condensed azine compounds such as quinolone compounds, isoquinoline compounds, quinoxaline compounds, quinazoline compounds, phenanthroline compounds, benzoquinoline compounds, benzoisoquinoline compounds, dibenzoquinoxaline compounds, preferably quinolone compounds, isoquinoline compounds, phenanthroline compounds; 5-membered heterocyclic compounds such as imidazole compounds, oxazole compounds, oxadiazole compounds, triazole compounds, thiazole compounds and thiadiazole compounds; condensed imidazole compounds such as benzimidazole compounds, imidazopyridine compounds, naphthoimidazole compounds, benzimidazolofenanthridine compounds, benzimidazolobenzimidazole compounds, preferably benzimidazole compounds, imidazopyridine compounds or benzimidazolofenanthridine compounds.

According to another embodiment, it is preferred that the electron transport layer comprises as Ar _p1 Ar _p2 Ar _P3 P=o.

Ar _p1 To Ar _p3 Is a substituent of a phosphorus atom and each independently represents a substituted or unsubstituted aryl group mentioned above or a substituted or unsubstituted heterocyclic group mentioned above.

According to another embodiment, it is preferred that the electron transport layer comprises an aromatic hydrocarbon compound. Specific examples of preferred aromatic hydrocarbon compounds for the electron transport layer are oligo-phenylene compounds, naphthalene compounds, fluorene compounds, fluoranthene groups, anthracene compounds, phenanthrene compounds, pyrene compounds, triphenylene compounds, benzanthracene compounds,Compounds, triphenylene compoundsCompounds, naphthacene compounds and benzol->The compound is preferably an anthracene compound, a pyrene compound, and a fluoranthene compound.

The hole blocking layer may be disposed adjacent to the emission layer and has a function of preventing leakage of holes from the emission layer to the electron transport layer. In order to improve the hole blocking ability, a material having a deep HOMO level is preferably used.

In a preferred embodiment, the organic electroluminescent device according to the invention comprises an electron transport region, wherein the electron transport region further comprises at least one of electron donating dopants and preferably at least one metal, metal complex or metal compound, wherein the at least one metal, metal complex or compound is preferably at least one selected from the group consisting of: alkali metal, alkali metal compound, alkali metal complex, alkaline earth metal compound, alkaline earth metal complex, rare earth metal compound, and rare earth metal complex. Suitable dopants are mentioned above.

More preferably, at least one of the electron donating dopants is at least one selected from the group consisting of: alkali metal, alkali metal compound, alkali metal complex, alkaline earth metal compound, alkaline earth metal complex, rare earth metal compound, and rare earth metal complex.

(cathode)

For the cathode, metals, alloys, conductive compounds, and mixtures thereof each having a small work function (specifically, a work function of 3.8eV or less) are preferably used. Specific examples of the material for the cathode include alkali metals such as lithium and cesium; alkaline earth metals such as magnesium, calcium and strontium; alloys containing these metals (e.g., magnesium-silver, aluminum-lithium); rare earth metals such as europium and ytterbium; alloys containing rare earth metals or aluminum.

The cathode is typically formed by vacuum vapor deposition or sputtering. In addition, in the case of using silver paste or the like, a coating method, an inkjet method, or the like may be employed.

In addition, when the electron injection layer is provided, the cathode may be formed using various conductive materials such as aluminum, silver, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide (which is selected independently of a work function) to form the cathode. These conductive materials are formed into films using sputtering, inkjet, spin coating, or the like.

(insulating layer)

In the organic EL device, pixel defects due to electric leakage or short circuit are easily generated due to the application of an electric field to the thin film. To prevent this, it is preferable to interpose an insulating thin layer between a pair of electrodes. Examples of the material used in the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. Mixtures thereof may be used for the insulating layer, and a laminate of layers containing these materials may also be used for the insulating layer.

(spacer layer)

The spacer layer is a layer disposed between the fluorescent emission layer and the phosphorescent emission layer in order to prevent excitons generated in the phosphorescent emission layer from diffusing to the fluorescent emission layer or in order to adjust carrier balance, for example, when the fluorescent emission layer and the phosphorescent emission layer are laminated. In addition, a spacer layer may be disposed between the plurality of phosphorescent light emitting layers.

Since the spacer layer is provided between the emission layers, for example, the material for the spacer layer is preferably a material having both electron transport ability and hole transport ability. In order to prevent the triplet energy from diffusing in the adjacent phosphorescent light emitting layer, it is preferable that the spacer layer has a triplet energy of 2.6eV or more. As a material for the spacer layer, the same materials as those for the hole transport layer mentioned above can be given.

(triplet Barrier layer)

A triplet blocking layer (exciton blocking layer) may be disposed adjacent to the emissive layer.

The triplet blocking layer has the following functions: triplet excitons generated in the emission layer are prevented from diffusing into an adjacent layer to trap the triplet excitons in the emission layer, thereby suppressing energy deactivation of the triplet excitons on molecules other than the emission dopant in the electron transport layer.

When a triplet blocking layer is provided in a phosphorescent device, the triplet energy of a phosphorescent dopant in an emission layer is denoted as ET d, and the triplet energy of a compound serving as a triplet blocking layer is denoted as ET TB. In the energy relationship of ET d < ET TB, triplet excitons of phosphorescent dopants are trapped (cannot transfer to another molecule) to leave no alternative pathway for energy deactivation other than emission on the dopant, so that highly efficient emission can be expected. However, when the energy gap (Δet=et TB-ET d) is small, even if the relationship of ET d < ET TB is satisfied, it is considered that the triplet exciton can be transferred to another molecule (independent of the energy gap Δet) by absorbing thermal energy around the device in an actual environment for driving the device (i.e., at about room temperature). In particular, since excitons of a phosphorescent device have a longer lifetime than excitons of a fluorescent device, they are more likely to be affected by heat absorption during exciton transfer on the phosphorescent device relative to the fluorescent device. The larger energy gap Δet with respect to the thermal energy at room temperature is preferably 0.1eV or more, more preferably 0.2eV or more. On the other hand, in a fluorescent device, the organic EL device material according to the exemplary embodiment may be used as a triplet blocking layer in the TTF device structure described in international publication WO2010/134350 A1.

(method for Forming layer)

The method for forming the respective layers of the organic EL device of the present invention is not particularly limited unless otherwise specified. Known film forming methods such as a dry film forming method, a wet film forming method, and the like can be used. Specific examples of the dry film forming method include vacuum deposition, sputtering, plasma, ion plating, and the like. Specific examples of the wet film forming method include various coating methods such as spin coating, dipping, flow coating, inkjet, and the like.

(film thickness)

The film thicknesses of the respective layers of the organic EL device of the present invention are not particularly limited unless otherwise specified. If the film thickness is too small, defects such as pinholes may occur, making it difficult to obtain sufficient brightness. If the film thickness is too large, a high driving voltage needs to be applied, resulting in a decrease in efficiency. In this regard, the film thickness is preferably 5nm to 10 μm, and more preferably 10nm to 0.2 μm.

(electronic apparatus (electronic device))

The present invention also relates to an electronic apparatus (electronic device) including the organic electroluminescent device according to the present application. Examples of the electronic apparatus include a display member such as an organic EL panel module; display devices for televisions, cell phones, smart phones, personal computers, and the like; and lighting devices for vehicle lighting devices.

It should be noted that the present invention is not limited to the above exemplary embodiments, but may include any modifications and improvements as long as such modifications and improvements are compatible with the present invention.

Examples

The following examples are included for illustrative purposes only and do not limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated.

I application example

Compounds for use in organic EL devices of application examples 1 to 15

/>

Compounds for use in organic EL devices of comparative application examples 1 to 4

Other Compounds used in organic EL devices of application examples 1 to 8 and comparative application examples 1 to 3

/>

Other Compounds used in the organic EL devices of application examples 9 to 15 and comparative application example 4

I application example

Application example 1

A glass substrate having a 130 nm-thick Indium Tin Oxide (ITO) transparent electrode (manufactured by Geomatec co., ltd.) as an anode was first treated with N ₂ Plasma treatment was performed for 100 seconds. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate support and loaded into a vacuum chamber. Thereafter, at about 10 ^-6 -10 ^-8 The organic material specified below is used at about mbarIs applied to the ITO substrate by vapor deposition. As hole injection layer, a mixture of 10 nm-thick compound HT-1 and 3% by weight of compound HI was applied. Then 80 nm-thick compound HT-1 and 5nm compound EB-1 were applied as hole transport layer and electron blocking layer, respectively. Subsequently, a mixture of 1 wt% of the emitter compound BD-1 and 99 wt% of the host compound BH-1 was applied to form a 20 nm-thick fluorescent-emitting layer. On this emission layer, 5 nm-thick compound HB was applied as a hole blocking layer and 25nm compound 1 as an electron transport layer. Finally, 1 nm-thick Yb was deposited as an electron injection layer, and then 50 nm-thick Al was deposited as a cathode to complete the device. The device was sealed with a glass cover and a getter in an inert nitrogen atmosphere with less than 1ppm of water and oxygen. To characterize an OLED, no record was made Electroluminescence spectrum at the same current and voltage. In addition, current-voltage characteristics were measured in combination with luminance to determine luminous efficiency and External Quantum Efficiency (EQE). At 10mA/cm ² Voltage and efficiency are reported. The results of the apparatus are shown in table 1.

The layer structure of the device is as follows:

ITO (130)/HT-1:HI=97:3 (10)/HT-1 (80)/EB-1 (5)/BD-1:BH-1=1:99 (20)/HB (5)/Compound 1 (25)/Yb (1)/Al (50).

Application example 2

Application example 1 was repeated except that compound 2 was used instead of compound 1 in the electron transport layer.

Application example 3

Application example 1 was repeated except that compound 3 was used instead of compound 1 in the electron transport layer.

Application example 4

Application example 1 was repeated except that compound 4 was used instead of compound 1 in the electron transport layer.

Comparative application example 1

Application example 1 was repeated except that comparative compound 2 was used instead of compound 1 in the electron transport layer.

TABLE 1

Application example	ET	Voltage (V)	LT95 (hours)
				Application example 1	Compound 1	3.5	200
Application example 2	Compound 2	3.7	270
				Application example 3	Compound 3	3.4	145
Application example 4	Compound 4	3.3	155
				Comparative application example 1	Comparative Compound 2	4.3	100

These results show that the voltage and lifetime are improved in the case of using the inventive compounds instead of the comparative compounds as electron transport materials in an OLED device with Yb as electron injection layer.

Application example 5

A glass substrate having a 130 nm-thick Indium Tin Oxide (ITO) transparent electrode (manufactured by Geomatec co., ltd.) as an anode was first treated with N ₂ Plasma treatment was performed for 100 seconds. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate support and loaded into a vacuum chamber. Thereafter, at about 10 ^-6 -10 ^-8 The organic material specified below is used at about mbarIs applied to the ITO base by vapor depositionA plate. As hole injection layer, a mixture of 10 nm-thick compound HT-1 and 3% by weight of compound HI was applied. Then 80 nm-thick compound HT-1 and 5nm compound EB-1 were applied as hole transport layer and electron blocking layer, respectively. Subsequently, a mixture of 1 wt% of the emitter compound BD-1 and 99 wt% of the host compound BH-1 was applied to form a 20 nm-thick fluorescent-emitting layer. On this emissive layer, 5 nm-thick compound HB was applied as a hole blocking layer and 25nm of compound 3 was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer, and then 50 nm-thick Al was deposited as a cathode to complete the device. The device was sealed with a glass cover and a getter in an inert nitrogen atmosphere with less than 1ppm of water and oxygen. To characterize an OLED, electroluminescence spectra at different currents and voltages were recorded. In addition, current-voltage characteristics were measured in combination with luminance to determine luminous efficiency and External Quantum Efficiency (EQE). At 10mA/cm ² Voltage and efficiency are reported. The results of the apparatus are shown in table 2.

The layer structure of the device is as follows:

ITO (130)/HT-1:HI=97:3 (10)/HT-1 (80)/EB-1 (5)/BD-1:BH-1=1:99 (20)/HB (5)/Compound 3 (25)/LiF (1)/Al (50).

Application example 6

Application example 5 was repeated except that compound 4 was used instead of compound 3 in the electron transport layer.

Comparative application example 2

Application example 5 was repeated except that comparative compound 1 was used instead of compound 1 in the electron transport layer.

TABLE 2

Application example	ET	Voltage (V)	EQE(％)	LT95 (hours)
					Application example 5	Compound 3	3.4	9.1	173
Application example 6	Compound 4	3.4	9.4	165
					Comparative application example 2	Comparative Compound 1	3.6	8.9	7

These results show that the voltage, efficiency and lifetime are improved in the case of using the inventive compounds instead of the comparative compounds as electron transport materials in OLED devices with LiF as electron injection layer.

Application example 7

A glass substrate having a 130 nm-thick Indium Tin Oxide (ITO) transparent electrode (manufactured by Geomatec co., ltd.) as an anode was first treated with N ₂ Plasma treatment was performed for 100 seconds. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate support and loaded into a vacuum chamber. Thereafter, at about 10 ^-6 -10 ^-8 The organic material specified below is used at about mbar Is applied to the ITO substrate by vapor deposition. As hole injection layer, a mixture of 10 nm-thick compound HT-1 and 3% by weight of compound HI was applied. Then 80 nm-thick compound HT-1 and 5nm compound EB-1 were applied as hole transport layer and electron blocking layer, respectively. Subsequently, a mixture of 1 wt% of the emitter compound BD-1 and 99 wt% of the host compound BH-1 was applied to form a 20 nm-thick fluorescent-emitting layer. On this emissive layer, 5 nm-thick compound HB was applied as a hole blocking layer and 20nm of 50 wt% compound 1 and lithium quinolinate (Liq) were applied as electron transport layers. Finally, 1 nm-thick Yb was deposited as an electron injection layer, and then 50 nm-thick Al was deposited as a cathode to complete the device. The device was sealed with a glass cover and a getter in an inert nitrogen atmosphere with less than 1ppm of water and oxygen. To characterize an OLED, electroluminescence spectra at different currents and voltages were recorded. In addition, current-voltage characteristics were measured in combination with luminance to determine luminous efficiency and External Quantum Efficiency (EQE). At 10mA/cm ² Voltage and efficiency are reported. The results of the apparatus are shown in table 3.

The layer structure of the device is as follows:

ITO (130)/HT-1:HI=97:3 (10)/HT-1 (80)/EB-1 (5)/BD-1:BH-1=1:99 (20)/HB (5)/Compound 1:Liq=50:50 (20)/Yb (1)/Al (50).

Application example 8

Application example 8 was repeated except that compound 4 was used instead of compound 1 in the electron transport layer.

Comparative application example 3

Application example 7 was repeated except that comparative compound 1 was used instead of compound 1 in the electron transport layer.

TABLE 3 Table 3

Application example	ET	Voltage (V)	LT95 (hours)
				Application example 7	Compound 1	3.2	179
Application example 8	Compound 4	3.2	159
				Comparative application example 3	Comparative Compound 1	3.2	79

Application example 9

A glass substrate having a 130 nm-thick Indium Tin Oxide (ITO) transparent electrode (manufactured by Geomatec co., ltd.) as an anode was first treated with N ₂ Plasma treatment was performed for 100 seconds. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate support and loaded into a vacuum chamber. Thereafter, at about 10 ^-6 -10 ^-8 The organic material specified below is used at about mbarIs applied to the ITO substrate by vapor deposition. As hole injection layer, a mixture of 10 nm-thick compound HT-2 and 3 wt.% of compound HI was applied. Then 80 nm-thick compound HT-2 and 5nm compound EB-2 were applied as hole transport layer and electron blocking layer, respectively. Subsequently, 4 wt% of the adhesive is appliedA mixture of an emitter compound BD-2 and 96 wt% of a host compound BH-2 to form a 25 nm-thick fluorescent-emitting layer. On this emissive layer, 5 nm-thick compound HB was deposited as a hole blocking layer and 20nm of compound 4 was deposited as an electron transport layer. Finally, 1 nm-thick Yb was deposited as an electron injection layer, and then 50 nm-thick Al was deposited as a cathode to complete the device. The device was sealed with a glass cover and a getter in an inert nitrogen atmosphere with less than 1ppm of water and oxygen. To characterize an OLED, electroluminescence spectra at different currents and voltages were recorded. In addition, current-voltage characteristics were measured in combination with luminance to determine luminous efficiency and External Quantum Efficiency (EQE). At 10mA/cm ² Voltage and efficiency are reported. The results of the apparatus are shown in table 1.

The layer structure of the device is as follows:

ITO (130)/HT-2:HI=97:3 (10)/HT-2 (80)/EB-2 (5)/BD-2:BH-2=4:96 (25)/HB (5)/Compound 4 (20)/Yb (1)/Al (50).

Application example 10

Application example 1 was repeated except that compound 5 was used instead of compound 4 in the electron transport layer.

Application example 11

Application example 1 was repeated except that compound 6 was used instead of compound 4 in the electron transport layer.

Application example 12

Application example 1 was repeated except that compound 7 was used instead of compound 4 in the electron transport layer.

Application example 13

Application example 1 was repeated except that compound 8 was used instead of compound 4 in the electron transport layer.

Application example 14

Application example 1 was repeated except that compound 9 was used instead of compound 4 in the electron transport layer.

Application example 15

Application example 1 was repeated except that compound 10 was used instead of compound 4 in the electron transport layer.

Comparative application example 1

Application example 1 was repeated except that comparative compound 3 was used instead of compound 4 in the electron transport layer.

TABLE 4 Table 4

Application example	ET	Voltage (V)	EQE(％)
				Application example 9	Compound 4	3.8	8.7
Application example 10	Compound 5	3.7	9.3
				Application example 11	Compound 6	3.7	8.9
Application example 12	Compound 7	3.8	8.8
				Application example 13	Compound 8	3.8	8.7
Application example 14	Compound 9	3.8	8.7
				Application example 15	Compound 10	3.7	8.9
Comparative application example 4	Comparative Compound 3	5.7	6.9

These results demonstrate that the lifetime is improved in the case of using the compounds of the invention instead of the comparative compounds as electron transport materials doped with lithium quinolinate in OLED devices.

Preparation example II

Compounds synthesized in preparation examples 1 to 10

/>

Compound 1

Into a 1L degassed 3-three neck round bottom flask was charged 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (20 g,51.5 mmol), (4-chlorophenyl) boronic acid (12.1 g,77 mmol), bis (triphenylphosphine) palladium chloride (0.36 g,0.51 mmol) and 2M aqueous sodium carbonate solution (64 mL,129 mmol). Toluene (260 mL) was then added and the reaction was heated at 60℃in an oil bath under nitrogen atmosphere for 16 hours. The reaction was then cooled to room temperature and the insoluble product was collected by filtration. The crude product was then dissolved in chloroform and filtered through a pad of silica, rinsing with chloroform. The solvent was evaporated under reduced pressure and the product was then suspended in acetone and allowed to stir at room temperature for 1 hour. The precipitate was then collected by filtration and dried. Intermediate 1 was then recrystallized from toluene to further purify the desired product (16.1 g,74% yield) as a white solid, which was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C27H18ClN 3=419, experimental value=420 (m+1)

To a 500mL pre-dried, degassed 3-neck round bottom flask was added intermediate 1 (16 g,38 mmol), dippinacolato-diboron (14.6 g,57.5 mmol), tris (dibenzyl acetone) dipalladium (0) (0.7 g,0.77 mmol), [ 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl ] (1.46 g,3.1 mmol), and potassium acetate (9.4 g,96 mmol). Dioxane (200 ml) was then added and the resulting reaction mixture was heated at an oil bath temperature of 90 ℃ overnight. The reaction mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The crude product was then dissolved in toluene and washed with water, saturated sodium bicarbonate and brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and methanol was added to the crude residue, and the mixture was stirred at room temperature for 1 hour. The precipitate was collected by filtration and dried. The product was then dissolved in toluene and filtered through a pad of silica, rinsed with toluene. Toluene was concentrated and the product was precipitated by slow addition of heptane. Intermediate 2 (10.5 g,54% yield) was isolated as a white solid and characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of c33h30bn3O 2=511, experimental value=512 (m+1)

5-bromo-1, 3-dihydro-2H-benzo [ d ] imidazol-2-one (2 g,9.39 mmol) was combined with methyl iodide (2.93 g,20.65 mmol) and potassium carbonate (5.19 g,37.6 mmol) in N, N-dimethylformamide (20 mL) and the reaction was stirred at room temperature overnight. The crude reaction mixture was poured onto water while stirring, and the precipitate thus formed was collected by filtration and dried. The product was then suspended in heptane and allowed to stir at room temperature for 1 hour, after which the precipitate was collected by filtration. Intermediate 3 (1.8 g,84% yield) was used without further purification and characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C8H7BrN2 o=226, experimental value=226 (m+)

The procedure for the synthesis of intermediate 1 was repeated except that intermediate 3 was used instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and intermediate 1 was used instead of (4-chlorophenyl) boric acid and palladium (II) acetate and [ 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl ] was used instead of bis (triphenylphosphine) palladium chloride. The obtained compound 1 (97% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry), the maximum ultraviolet absorption wavelength in toluene (UV (PhMe) λonset) and the maximum fluorescence wavelength in toluene (FL (PhMe, λex=330 nm) λmax). The results are shown below.

ESI-MS: theoretical value of C36H27N5 o=545, experimental value=545 (m+)

UV(PhMe)λonset：393nm

FL(PhMe，λex＝330nm)λmax：433nm

Compound 2

Aniline (10.00 ml,107 mmol) was combined with 4-bromo-1-fluoro-2-nitrobenzene (13.27 ml,107 mmol) and potassium carbonate (17.81 g,129 mmol) in dioxane/water (200 ml, 1:1) and the mixture was heated at reflux overnight. The reaction was cooled to room temperature and dioxane was removed under reduced pressure. Ethyl acetate was then added and the aqueous phase was removed. The organic phase was then further washed with brine and dried over magnesium sulfate, and the solvent was evaporated to give the crude product. The product was then dissolved in tetrahydrofuran/water (200 mL, 1:1) and ammonium chloride (51.9 g,970 mmol) was added. The mixture was cooled in a water/ice bath and zinc (31.7 g, 480 mmol) was added in portions. The reaction was allowed to warm to room temperature while stirring overnight. Insoluble precipitate was removed by filtration, and the mother liquor was diluted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate and water, dried over magnesium sulfate and the solvent was removed under reduced pressure. Crude intermediate 4 (23.7 g,81% yield) was used without further purification and characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C12H11BrN 2=262, experimental value=263 (m+1)

Intermediate 4 (21, 23g,62.1 mmol) was dissolved in tetrahydrofuran (200 mL) at room temperature under nitrogen. 1,1' -carbonyldiimidazole (10.45 g,62.1 mmol) was added in portions and the reaction was stirred at room temperature overnight. THF was removed under reduced pressure, and the precipitate thus formed was collected by filtration. The crude precipitate was then suspended in diethyl ether and allowed to stir at room temperature for 1 hour. The precipitate was then collected by filtration and dried. Intermediate 5 (9.8 g,55% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C13H9BrN2 o=288, experimental value=289 (m+1)

The procedure for the synthesis of intermediate 3 was repeated except that intermediate 5 was used instead of 5-bromo-1, 3-dihydro-2H-benzo [ d ] imidazol-2-one. Intermediate 6 (94% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C14H11BrN2 o=302, experimental value=302 (m+)

The procedure for the synthesis of compound 1 was repeated except that intermediate 6 was used instead of intermediate 3. The compound 2 obtained (90% yield) was characterized by ESI-MS, maximum ultraviolet absorption wavelength in toluene (UV (PhMe) λonset) and maximum fluorescence wavelength in toluene (FL (PhMe, λex=330 nm) λmax). The results are shown below.

ESI-MS: theoretical value of C41H29N5 o=607, experimental value=607 (m+)

UV(PhMe)λonset:390nm

FL(PhMe，λex＝330nm)λmax:433nm

Compound 3

The procedure for the synthesis of intermediate 4 was repeated but with pyridin-2-amine instead of aniline and potassium tert-butoxide instead of potassium carbonate and tetrahydrofuran instead of dioxane/water. Intermediate 7 (85% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value=263, experimental value=262 (m-1) of C11H10BrN3

The procedure for the synthesis of intermediate 5 was repeated except that intermediate 7 was used instead of intermediate 4. Intermediate 8 (33% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C12H8BrN3 o=289, experimental value=288 (m-1)

The procedure for the synthesis of intermediate 6 was repeated except that intermediate 8 was used instead of intermediate 5. Intermediate 9 (98% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C13H10BrN3 o=303, experimental value=304 (m+1)

The procedure for the synthesis of compound 1 was repeated except that intermediate 9 was substituted for intermediate 3. The compound 3 obtained (79% yield) was characterized by ESI-MS, maximum ultraviolet absorption wavelength in toluene (UV (PhMe) λonset) and maximum fluorescence wavelength in toluene (FL (PhMe, λex=330 nm) λmax). The results are shown below.

ESI-MS: theoretical value of C40H28N6 o=608, experimental value=609 (m+1)

UV(PhMe)λonset:390nm

FL(PhMe，λex＝330nm)λmax:426nm

Compound 4

The procedure used for the synthesis of intermediate 1 was repeated except that 2-chloro-4- (9, 9-diphenyl-9H-fluoren-4-yl) -6-phenyl-1, 3, 5-triazine was used instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. Intermediate 10 (87% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C40H26ClN 3=583, experimental value=584 (m+1)

The procedure for the synthesis of intermediate 2 was repeated except that intermediate 10 was used instead of intermediate 1. Intermediate 11 (59% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C46H38BN3O 2=675, experimental value=675 (m+)

The procedure for the synthesis of compound 1 was repeated except that intermediate 11 was substituted for intermediate 2. The compound 4 obtained (82% yield) was characterized by ESI-MS, maximum ultraviolet absorption wavelength in toluene (UV (PhMe) λonset) and maximum fluorescence wavelength in toluene (FL (PhMe, λex=330 nm) λmax). The results are shown below.

ESI-MS: theoretical value of C40H28N6 o=709, experimental value=710 (m+1)

UV(PhMe)λonset:395nm

FL(PhMe，λex＝330nm)λmax:425nm

Comparative Compound 1

The procedure used for the synthesis of intermediate 1 was repeated except that 2, 4-bis ([ 1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine was used instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and (3, 4-dichlorophenyl) boronic acid was used instead of (4-chlorophenyl) boronic acid. Intermediate 12 (97% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C33H21Cl2N 3=529, experimental value=530 (m+1)

Intermediate 12 (7, 32g,13,80 mmol) was combined with 4-methoxyaniline (4, 08g,33,1 mmol) in a 250mL degassed 3-neck round bottom flask and tris (dibenzylideneacetone) dipalladium (0) (0.12 g,0.14 mmol), [ 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl ] (0.13 g,0.27 mmol) was added followed by cesium carbonate (11.7 g,36 mmol). Toluene (150 mL) was then added and the reaction mixture was heated at reflux overnight. The reaction was then cooled to room temperature and the precipitate was collected by filtration. The precipitate was then dissolved in dichloromethane and washed with saturated aqueous sodium bicarbonate, water and brine, dried over magnesium sulfate and the solvent removed under reduced pressure. The crude product was suspended in methanol and allowed to stir at room temperature for 1 hour, then the precipitate was collected by filtration and dried. Intermediate 12 (7.5 g,77% yield) was characterized by ESI-MS (electrospray ionization mass spectrometry). The results are shown below.

ESI-MS: theoretical value of C47H37N5O 2=703, experimental value=702 (m-1)

Intermediate 13 (3 g,4.3 mmol) was combined with 1,1' -carbonyldiimidazole (2.2 g,12.8 mmol) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (1.9 g,12.8 mmol) in tetrahydrofuran (120 mL) and the resulting reaction mixture was heated at reflux overnight. The reaction was then cooled to room temperature and the crude product was collected by filtration and washed with hot THF. Comparative compound 1 (2.2 g,69% yield) was characterized by ESI-MS and 1H NMR. The results are shown below.

ESI-MS: theoretical value of C48H35N5O 3=729, experimental value=730 (m+1)

1H NMR (300 MHz, dichloromethane-d 2) delta 8.86-8.75 (m, 4H), 8.69 (m, 1H), 8.49 (d, J=1.5 Hz, 1H), 7.93-7.82 (m, 4H), 7.82-7.74 (m, 4H), 7.71-7.63 (m, 2H), 7.63-7.40 (m, 8H), 7.28-7.09 (m, 5H), 3.98 (s, 3H), 3.95 (s, 3H).

Compound 5

In a 500mL three-necked round bottom flask was placed 4-chloro-6- (9, 9-diphenyl-9H-fluoren-2-yl) -2-phenylpyrimidine (9.28 g,18.30 mmol) followed by 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -1, 3-dihydro-2H-benzo [ d ]]Imidazol-2-one (8.00 g,21.96 mmol) and Pd (PPh) ₃ ) ₄ (0.846 g,0.73 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (183 ml) and 2M Na ₂ CO ₃ aq. (23 ml) was added to the mixture and heated to 90 ℃ overnight. The reaction mixture was cooled to RT and the solvent was evaporated. Crude material with MeOH and H ₂ O was washed and purified by silica gel chromatography with hexane and CH ₂ Cl ₂ Compound 5 was eluted as a white solid (11.98 g,87% yield).

As a result of mass spectrometry analysis, m/e=709 was found and this compound was identified as the above-mentioned compound 5 (accurate mass: 708.28).

Compound 6

In a 500mL three-necked round bottom flask was placed 4- ([ 1,1' -biphenyl) ]-4-yl) -6- (4-bromophenyl) -2-phenylpyrimidine (7.00 g,15.11 mmol) followed by 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1, 3-dihydro-2H-benzo [ d ]]Imidazol-2-one (6.53 g,22.66 mmol) and Pd (PPh) ₃ ) ₄ (1.05 g,0.91 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (151 ml) and 2M Na ₂ CO ₃ aq. (19 ml) was added to the mixture and heated to 90 ℃ overnight. The reaction mixture was cooled to RT and MeOH was added. The resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was then dissolved in toluene and filtered through a pad of silica, rinsed with CH2Cl 2/meoh=95/5 (v/v),compound 6 was obtained as a white solid (8.23 g,88% yield).

As a result of mass spectrometry analysis, m/e=545 was found and this compound was identified as the above-mentioned compound 6 (accurate mass: 544.23).

Compound 7

In a 500mL three-necked round bottom flask was placed 4- (4-bromophenyl) -6- (4-chlorophenyl) -2-phenylpyrimidine (10.00 g,23.71 mmol) followed by dibenzo [ b, d ]]Furan-3-ylboronic acid (5.03 g,23.71 mmol) and Pd (PPh) ₃ ) ₄ (0.82 g,0.71 mmol). The mixture was evacuated and backfilled 3 times with argon. DME (337 ml) and 2M Na2CO3 aq (30 ml) were added to the mixture and heated at reflux for 8h. The reaction mixture was cooled to RT and the solvent was evaporated. Crude material with MeOH and H ₂ O was washed, then dissolved in toluene and filtered through a pad of silica, rinsed with toluene. The resulting pale yellow solid was purified by recrystallization from toluene to afford intermediate 14 as a white solid (8.06 g,67% yield).

As a result of mass spectrometry analysis, m/e=509 was found and this compound was identified as the above intermediate 14 (accurate mass: 508.13).

Compound 7

In a 250mL three-necked round bottom flask was placed intermediate 14 (5.09 g,10.00 mmol) followed by 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1, 3-dihydro-2H-benzo [ d ]]Imidazol-2-one (3.17 g,11.00 mmol), pd2 (dba) 3 (0.18 g,0.20 mmol) and Amphos (0.21 g,0.80 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (67 ml) and 2M Na ₂ CO ₃ aq. (15 ml) was added to the mixture and heated under reflux for 6h. The reaction mixture was cooled to RT and the resulting precipitate was passed throughCollected by filtration and purified by MeOH and H ₂ And (3) washing. The crude material was then dissolved in toluene/ethyl isobutyrate=3/1 (v/v) and filtered through a silica pad, rinsed with toluene/ethyl isobutyrate=3/1 (v/v). After removal of the solvent, the crude material was purified by recrystallisation from toluene to give compound 7 as a white solid (5.29 g,83% yield).

As a result of mass spectrometry analysis, m/e=635 was found and this compound was identified as the above-described compound 7 (accurate mass: 634.24).

Compound 8

In a 1000mL three-necked round bottom flask was placed 4- (4-bromophenyl) -2, 6-diphenylpyrimidine (12.00 g,31.00 mmol) followed by anthracene-9-yl boronic acid (7.57 g,34.1 mmol) and Pd (PPh 3) 4 (1.43 g,1.24 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (310 ml) and 2M Na ₂ CO ₃ aq. (47 ml) was added to the mixture and heated at reflux for 7h. The reaction mixture was cooled to RT and H ₂ O was added to the mixture. The resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was dissolved in toluene and filtered through a pad of silica, rinsed with toluene. The resulting yellow solid was purified by recrystallization from toluene to afford intermediate 15 as a pale yellow solid (11.28 g,75% yield).

As a result of mass spectrometry analysis, m/e=485 was found and this compound was identified as intermediate 15 described above (exact mass: 484.19).

/>

In a 1000mL three-necked round bottom flask was placed intermediate 15 (10.50 g,21.67 mmol) followed by NBS (3.83 g,21.50 mmol). The mixture was evacuated and backfilled 3 times with argon. DMF (430 ml) was added to the mixture and heated to 50deg.C for 3h. The reaction mixture was cooled to RT and H ₂ O was added to the mixture. The resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was dissolved in toluene and filtered through a pad of silica, rinsed with toluene. The yellow solid obtained was purified by chromatography on silica gel, using hexane and CH ₂ Cl ₂ Eluting and further purifying by recrystallisation from toluene, provided intermediate 16 as a pale yellow solid (8.44 g,69% yield).

As a result of mass spectrometry, m/e=563 was found and this compound was identified as the above intermediate 16 (accurate mass: 562.10).

In a 250mL three-necked round bottom flask was placed intermediate 16 (5.63 g,10.00 mmol), followed by 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1, 3-dihydro-2H-benzo [ d ]]Imidazol-2-one (3.17 g,11.00 mmol), pd ₂ (dba) ₃ (0.18 g,0.20 mmol) and Amphos (0.21 g,0.80 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (67 ml) and 2M Na ₂ CO ₃ aq. (15 ml) was added to the mixture and heated under reflux for 6h. The reaction mixture was cooled to RT and the resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was then dissolved in chlorobenzene and filtered through a pad of silica, using chlorobenzene, toluene and CH ₂ Cl ₂ Meoh=95/5 (v/v) rinse. After removal of the solvent, compound 8 was obtained as a yellow solid (3.41 g,53% yield).

As a result of mass spectrometry analysis, m/e=645 was found and this compound was identified as the above-described compound 8 (accurate mass: 644.26).

Compound 9

At 500mL three-necked round bottomThe flask was charged with 4- (4-bromophenyl) -6- (4-chlorophenyl) -2-phenylpyrimidine (8.20 g,19.44 mmol) followed by (10-phenylanthracen-9-yl) boronic acid (9.28 g,31.10 mmol) and Pd (PPh 3) 4 (1.12 g,0.97 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (194 ml) and 2M Na ₂ CO ₃ aq. (24 ml) was added to the mixture and heated at reflux for 7h. The reaction mixture was cooled to RT and the resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was dissolved in toluene and filtered through a pad of silica, rinsed with toluene. The resulting yellow solid was washed with ethyl acetate to afford intermediate 17 as a pale yellow solid (8.06 g,70% yield).

As a result of mass spectrometry, m/e=595 was found and this compound was identified as intermediate 17 described above (exact mass: 594.18).

In a 300mL three-necked round bottom flask was placed intermediate 17 (8.00 g,13.44 mmol) followed by 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -1, 3-dihydro-2H-benzo [ d ] ]Imidazol-2-one (5.04 g,17.47 mmol), pd2 (dba) 3 (0.25 g,0.27 mmol), and Xphos (0.44 g,1.08 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (134 ml) and 2M Na ₂ CO ₃ aq. (17 ml) was added to the mixture and heated at reflux for 7h. The reaction mixture was cooled to RT and MeOH was added to the mixture, then the resulting precipitate was collected by filtration and purified by filtration with MeOH and H ₂ And (3) washing. The crude material was dissolved in chlorobenzene and filtered through a pad of silica, using chlorobenzene and CH ₂ Cl ₂ Meoh=95/5 (v/v) rinse. After removal of the solvent, the crude material was washed with toluene to give compound 9 as a pale yellow solid (7.52 g,78% yield).

As a result of mass spectrometry analysis, m/e=721 was found and this compound was identified as the above-mentioned compound 9 (accurate mass: 720.29).

Compound 10

In a 500mL three-necked round bottom flask was placed 4- ([ 1,1' -biphenyl)]-4-yl-d 9) -6-chloro-2-phenylpyrimidine (2.00 g,5.68 mmol) was then added 1, 3-dimethyl-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -1, 3-dihydro-2H-benzo [ d ]]Imidazol-2-one (2.48 g,6.82 mmol) and Pd (PPh) ₃ ) ₄ (0.26 g,0.23 mmol). The mixture was evacuated and backfilled 3 times with argon. 1, 4-dioxane (57 ml) and 2M Na ₂ CO ₃ aq. (7 ml) was added to the mixture and heated to 90 ℃ overnight. The reaction mixture was cooled to RT and MeOH was added. The resulting precipitate was collected by filtration and purified with MeOH and H ₂ And (3) washing. The crude material was then dissolved in toluene and filtered through a pad of silica, using CH ₂ Cl ₂ Meoh=95/5 (v/v) rinse to give compound 10 as a white solid (2.5 g,79% yield).

As a result of mass spectrometry analysis, m/e=554 was found and this compound was identified as the above-mentioned compound 10 (accurate mass: 553.28).

Claims

1. A compound represented by formula (I):

wherein the method comprises the steps of

Y represents NR ¹⁰ 、CR ⁸ R ⁹ O or S, preferably NR ¹⁰ ；

R ⁸ and R is ⁹ Each independently represents hydrogen, containing 6 to 30 cyclic precursorsUnsubstituted or substituted aromatic hydrocarbon groups of the sub-group or unsubstituted or substituted heteroaryl groups containing 3 to 30 ring atoms, unsubstituted or substituted alkyl groups having 1 to 25 carbon atoms or unsubstituted or substituted cycloalkyl groups having 3 to 18 ring carbon atoms;

Or alternatively

wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of which is a bonding site;

X ¹ Represents N or CR ¹¹ ；

X ² Represents N or CR ¹² ；

X ³ Represents N or CR ¹³ ；

or alternatively

2. A compound according to claim 1, wherein Y represents NR ¹⁰ 。

3. The compound according to claim 1 or 2, wherein R ¹ And R is ² Each independently represents hydrogen, an unsubstituted or substituted aromatic hydrocarbon group containing 6 to 30 ring atoms, or an unsubstituted or substituted heteroaryl group containing 3 to 30 ring atoms.

4. A compound according to claims 1 to 3, wherein R ¹ And R is ² Each independently represents an unsubstituted aromatic hydrocarbon group having 6 to 30 ring atoms, an aromatic hydrocarbon group having 6 to 30 ring atoms substituted with an aromatic hydrocarbon group having 6 to 30 ring atoms, an aromatic hydrocarbon group having 6 to 30 ring atoms substituted with a heteroaryl group having 3 to 30 ring atoms, or an unsubstituted heteroaryl group having 3 to 30 ring atoms.

5. According to claim1 to 4, wherein R ¹ And R is ² Each independently represents an unsubstituted aromatic hydrocarbon group having 6 to 30 ring atoms, an aromatic hydrocarbon group having 6 to 30 ring atoms substituted with a dibenzofuranyl group or a dibenzothiophenyl group, an unsubstituted dibenzofuranyl group or an unsubstituted dibenzothiophenyl group.

6. The compound according to any one of claims 1 to 5, wherein R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ Is hydrogen, wherein R ⁴ 、R ⁵ 、R ⁶ And R is ⁷ One of which is a bonding site.

7. The compound according to any one of claims 1 to 6, wherein R ³ And R is ¹⁰ Each independently represents an unsubstituted or substituted aromatic hydrocarbon group having 6 to 18 ring atoms, an unsubstituted or substituted heteroaryl group having 3 to 18 ring atoms, an unsubstituted or substituted cycloalkyl group having 5 to 8 ring carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms.

8. The compound of claim 7, wherein R ³ And R is ¹⁰ Each independently represents methyl, ethyl, n-propyl, isopropyl, phenyl, naphthyl, pyridinyl or quinoline.

9. A compound according to any one of claims 1 to 8, wherein L represents an unsubstituted or substituted divalent aromatic hydrocarbon group containing 6 to 24 ring atoms, preferably 6 to 18 ring atoms, or an unsubstituted or substituted divalent heteroaryl group containing 3 to 24 ring atoms, preferably 3 to 18 ring atoms; more preferably, L represents an unsubstituted or substituted divalent phenyl group, an unsubstituted or substituted divalent naphthyl group, an unsubstituted or substituted divalent anthryl group, an unsubstituted or substituted phenanthryl group, an unsubstituted or substituted triphenylene group, a 9, 9-dimethylfluorenyl group, an unsubstituted or substituted 9, 9-diphenylfluorenyl group, or an unsubstituted or substituted divalent heteroaryl group containing 3 to 24 ring atoms, preferably 3 to 14 ring atoms; most preferably, the unsubstituted 1, 4-phenylene group, unsubstituted 1, 3-phenylene group, 1, 4-phenylene group substituted with phenyl, naphthyl or phenanthryl group, 1, 3-phenylene group substituted with phenyl, naphthyl or phenanthryl group, unsubstituted 1, 4-naphthylene group, unsubstituted 1, 5-naphthylene group, unsubstituted 1, 6-naphthylene group, unsubstituted 2,7-9, 9-diphenyl-fluorene, unsubstituted 2,5-9, 9-diphenyl-fluorene, unsubstituted 2,7-9, 9-dimethyl-fluorene, unsubstituted 2,5-9, 9-dimethyl-fluorene, unsubstituted 2, 7-triphenylene, unsubstituted 9, 10-anthracenyl group, substituted 9, 6-anthracenyl group, substituted 9, 7-anthracenyl group, or unsubstituted divalent heteroaryl group containing 3 to 24 ring atoms, preferably 3 to 14 ring atoms.

10. The compound according to any one of claims 1 to 9, wherein the group- (L) _m -represented by:

wherein the dashed line is the bonding site.

11. A compound according to any one of claims 1 to 3, wherein R ₁ And R is ₂ Each is a substituted or unsubstituted group selected from the following formulas:

wherein any group is omitted and the dotted line is the bonding site.

12. A compound according to any one of claims 1 to 3, wherein R ¹ And R is ² Each more preferably is a substitution or substitution selected from the following formulaeUnsubstituted group:

wherein any group is omitted and the dotted line is the bonding site.

13. A material for an organic electroluminescent device, the material comprising at least one compound according to any one of claims 1 to 12.

14. An organic electroluminescent device comprising at least one compound according to any one of claims 1 to 12, preferably comprising a cathode, an anode and one or more organic thin film layers comprising an emissive layer arranged between the cathode and the anode, wherein at least one of the organic thin film layers comprises at least one compound according to any one of claims 1 to 12.

15. The organic electroluminescent device according to claim 14, wherein the organic thin film layer comprises an electron transport region disposed between the emissive layer and the cathode, wherein the electron transport region comprises at least one compound according to any one of claims 1 to 12.

16. The organic electroluminescent device according to claim 15, wherein the electron transport region comprises an electron transport layer disposed between the emissive layer and the cathode, wherein the electron transport layer comprises at least one compound according to any one of claims 1 to 12.

17. The organic electroluminescent device according to claims 15 to 16, wherein the electron transport region further comprises at least one metal, metal complex or metal compound, wherein the at least one metal, metal complex or metal compound is preferably at least one selected from the group consisting of: alkali metal, alkali metal compound, alkali metal complex, alkaline earth metal compound, alkaline earth metal complex, rare earth metal compound, and rare earth metal complex.

18. An electronic device comprising the organic electroluminescent apparatus according to any one of claims 14 to 17.

19. Use of a compound of formula (I) according to any one of claims 1 to 12 in an organic electroluminescent device, wherein the organic electroluminescent device preferably comprises a cathode, an anode and one or more organic thin film layers comprising an emissive layer arranged between the cathode and the anode, wherein the organic thin film layers more preferably comprise an electron transport region arranged between the emissive layer and the cathode, wherein most preferably the electron transport region comprises at least one compound according to any one of claims 1 to 12.